Best Album Openers...

Pixies - 'Debaser' on Doolittle
The Who Baba O'reily on Who’s Next
Radiohead - Everything in its Right Place on Kid A
David Bowie - 'Five Years' on The Rise and Fall of Ziggy Stardust and the Spiders from Mars
I was thinking Pixies myself but I couldn't decide between Doolittle or Surfer Rosa.
Violent Femmes first album would probably be a contender too.
Summer Babe from Slanted and Enchanted as well.
There are too many to list.

Enter Sandman - Metallica - Metallica
Weight of love - Turn Blue - The Black Keys
Do I wanna know - AM - Arctic Monkeys
Each and everyone - Eden - Everything but the Girl
Driving - Language of life - EBTG
Slow night, so long - Aha Shake Heartbreak - Kings of Leon
By the way - By the way - Red Hot Chili Peppers
Spellbound - Juju - Siouxsie & The Banshees
Intro - XX - The XX
One hundred years - Pornography - The Cure
Head Like a Hole (Pretty Hate Machine) - Nine Inch Nails
Plainsong (Disintegration) - The Cure
World In My Eyes (Depeche Mode) - Violator

Agree about Welcome to the `jungle and Stone Roses - Adored
"The Changeling" L A Woman,
A boyfriend of my older sister bought her this album for her birthday,
after the opening few bars i was hooked on the doors for life.