Man, SRV's version of little wing is definatley my vote. I absolutely love anytime a song sends shivers up and down my spine. Here's a few other songs that have done that to me:

Dire Straits - "Sultans of Swing" (the triplets at the end)
GNR - "November Rain" (That last solo made me buy a guitar)
Audioslave - "I am the highway" and "Getaway Car"