There are great song intros.
Leaving plenty of room for more
Good list. Got 70% of those.
I'll go with Keb Mo, 'Soon as I get paid'. Starts all country picky, then blasts off into a great blues rhythm.
Jo Cocker, 'Space Captain'
Joe Diffie, 'John Deere Green'. Starts cheesy, gets cheesier. Brilliant.
'Stepping Out', Clapton with Mayall on 'Bluesbreakers'. Starts tight then just rips up the frets.
John Lee Hooker and Van Morrison, 'I Cover the Waterfront'. Starts sad gets wistful. Then the resolution.
Macy Gray, 'I Try', Best she ever did.
'Different Class' by Pulp. Serious message after a contrived start.
'Six Days on the Road'. Taj Mahal, from Giant Step. I can't hear that without seeing a huge Kenworth with two plumes of diesel smoke driving over the Rockies.
Now for something completely different:
Fantasia on a theme by Thomas Tallis, by Vaughan Williams. You check to see if the amp is still on, then it sneaks up on you.
Lastly,
Days Rheingold, Wagner. You can hear the earth waking up in the overture.