Needles in the Camel's Eyes - ENO - Here Come the Warm Jets

Disorder - Joy Division - Unknown Pleasures

'And It Stoned Me' Moondance

Thirded.

Highway To Hell. The most powerful "a" chord of all time.

Rage Against the Machine - Evil Empire - People of the Sun
Weezer - Weezer - My Name is Jonas

Detroit Rock City

prince - let's go crazy, off the purple rain soundtrack.
prince - p. control, off gold.
prince - 1999, off 1999.

Politik - Coldplay
Square One - Coldplay
Jenny Was A Friend of Mine - The Killers
Devil In a Midnight Mass - Billy Talent
This is How it Goes - Billy Talent

Ill add more laer

Astral Weeks - Van Morrison

Coincidentally, this will be the topic of this week's episode of Sound Opinions:

http://www.soundopinions.org/

Angel of Death- Slayer

Blind- Korn

Cherub Rock- Smashing Pumpkins

Refuse/Resist- Sepultura

Where Eagles Dare- Iron Maiden

Opaline- Dishwalla

Butthole Surfers - Locust Abortion Technician
Side 1 Track 1 "Sweat Loaf"
Silence, more silence...is there something wrong with the needle? Wait, there's some strings, sounds like a Mantovani record. Someone's talking...WTF is with that voice? Is he trying to sound like Zappa? What is th-SATAN!!!!!!! Aaah, shit that was scary...and Christ, those drums sound like bombs! Wait, is this a Sabbath cover? From that point I was hooked.

Electric Eels - God Says Fuck You
Track 1 "Agitated"
A wordless vocal bellow that sounds disturbingly like a drunk hobo thrown out of an airplane while masturbating. Then a guitar riff so ugly and loud that it threatens to burn your nosehairs. Then a drum kit is kicked down a flight of stairs and back up again. When it gets to the word "agitated" in the chorus, the singer draws out seven syllables of the "ah" sound like he's choking on a tongue depressor. A song so brutish and offensive that it dares you to stop listening.

The Frogs - It's Only Right and Natural
Side 1 Track 1 "i've got drugs (out of the mist)"
A voice that could only come from a diseased pervert intones, "I've done drugs....that'll blow your mind tonight..." A gentle guitar jangles along, gradually overtaken by the buzz of feedback. Vocals overlap and drift around in the mix like half remembered daydreams. Then the phrase "fuckin' priest with a yeast infection" punches through the mush in a remarkably catchy way. And before the song has even started, it's over - but you're compelled to listen to the rest of the record...and then take a bath.

-Tom Cochrane: "The Boy Inside the Man" (Tom Cochrane & Red Rider (1986))
-Asia: "Heat of the Moment" (Asia (1982))
-Bruce Cockburn: "When You Give it Away" (Breakfast in New Orleans, Dinner... (1999)), "Lovers in a Dangerous Time" (Stealing Fire (1984)), "Call it Democracy" (World of Wonders (1986))
-Marc Cohn: "Walking in Memphis" (Marc Cohn (1992))
-Genesis: "Invisible Touch" (Invisible Touch (1986))
-Dream Academy: "Life in a Northern Town" (Dream Academy (1985))
-Hooters: "And We Danced" (Nervous Night (1985)), "Satellite" (One Way Home (1987)), "Brother Don't You Walk Away" (Zig Zag (1989))
-Marillion: "Cover My Eyes" (Holidays in Eden (1991))
-Barry McGuire: "Eve of Destruction" (Eve of Destruction (1965))
-Tom Petty: "Free Fallin'" (Full Moon Fever (1989))
-Rubinoos: "Amnesia" (Paleophonic (1998))
-Bob Seger: "American Storm" (Like a Rock (1986))
-The Seventh Key: "The Sun Will Rise" (The Raging Fire (2004))
-Springsteen: "Badlands" (Darkness on the Edge of Town (1978))
-Cat Stevens: "The Wind" (Teaser and the Firecat (1971))
-Strange Advance: "She Controls Me" (Worlds Away (1983))

I liked it better when it kicked off Stevie Ray Vaughan's "In Step," but Setzer's cover is good, too.

I'll go with "Where the Streets Have No Name" from U2's "The Joshua Tree."

One Of These Days - Pink Floyd

A few that are not just the opening tracks of albums, but the opening tracks of debut albums:

Break on Through -- The Doors
Blitzkrieg Bop -- The Ramones
Gloria -- Patti Smith
Twice as Hard -- Black Crowes

Where the Streets Have No Name - U2 The Joshua Tree

Nirvana - Serve the Servants. The line 'Teenage angst has paid off well, now I'm bored & old' is THE greatest opening line ever.

Bruce Springsteen - Thunder Road. This is textboox song imagery & without opening with this track, Born to Run would be a much weaker album.

Cheap Trick - Hello There. From In Color. Of course.

Press Play - Stone Temple Pilots - Tiny Music... Songs From The Vatican Gift Shop

Hell yeah! Badlands and Nebraska (the opening tracks to Darkness on the Edge of Town and Nebraska, respectively) are two more great first songs.

Back in the day before the intertubes, if I heard a recommendation for an album (via a magazine, friend, etc) it was almost impossibe to actually hear the album until I got home. So hearing that first track for the first time and having it floor me was always a big thrill. I also like opening tracks that set a tone or subvert/destroy any ideas you might have had about a band or just in general cause you to stop what you're doing and listen to what's going on with the music.

Fiona Apple - "Sleep to Dream" from Tidal
Arcade Fire - "Neighborhood #1 (Tunnels)" from Funeral
Arcade Fire - "Black Mirror" from Neon Bible
B. Fleischmann - "Start" from Choir of Empty Beds
The Beatles - "Back in the USSR" from The White Album
Björk - "Army of Me" from Post
Bright Eyes - "At the Bottom of Everything" from I'm Wide Awake, It's Morning
Cannibal Ox - "Iron Galaxy" from The Cold Vein
Clinic - "Harmony" from Walking With Thee
Coldplay - "Politik" from A Rush of Blood to the Head
The Doors - "The Changeling" from L.A. Woman
Jurgen Paape - "So Weit Wie Noch Nie" from DJ Kicks: Erlend_Øye
Kasabian - "Club Foot" from the self-titled
The Kils - "No Wow" from No Wow
Le Tigre - "Deceptacon" from the self-titled
Magnetic Fields - "Absolutely Cuckoo" from 69 Love Songs
Nazareth - "Hair of the Dog" from Hair of the Dog
Neu! - "Isi" from Neu! 75
Placebo - "Pure Morning" from Without You I'm Nothing
Pulp - "The Fear" from This is Hardcore
Queens of the Stone Age - "You Think I Ain't Worth a Doll" from Songs for the Deaf
Radiohead - "Everything In It's Right Place" from Kid A
TV On The Radio - "The Wrong Way" from Desperate Youth, Bloodthirsty Babes
Yerba Buena - "Guajira (I Love U 2 Much)" from President Alien
Yo La Tengo - "Pass the Hatchet, I Think I'm Goodkind" from I Am Not Afraid of You and I Will Beat Your Ass

And these sort of don't count because they have intros in front of them, but:

Peter, Bjorn and John - "Objects of My Affection" from Writer's Block
Wu-Tang Clan - "Reunited" from Wu-Tang Forever

Heard bits and pieces of Sound Opinions while I was running some errands tonight. Three great picks they mentioned that haven't been listed in this thread:

Cinnamon Girl -- Everyboyd Knows This Is Nowhere, Neil Young
Smells Like Teen Spirit -- Nevermind, Nirvana
Straight Outta Compton -- Straight Outta Compton, NWA

HYPERPOWER! on Year Zero.

Hello Hooray, From Alice Cooper Billion Dollar Babies

DIO - Stand up and Shout
Black Sabbath - Neon Knights
Iron Maiden - Where Eagles Dare
KISS - I've Had Enough
KISS - Unholy
KISS - Creatures of the Night
KISS - Strutter
Thin Lizzy - Jailbreak
Scorpions - Blackout
Armored Saint - Reign of Fire
Def Leppard - Let it Go
Ozzy Osbourne/Randy Rhoads - Over the Mountain
Saxon - Killing Ground
Judas Priest - Hellion/Electric Eye

Those are some great opening tracks just off the top of my head...