Well, if held to one choice, it would have to be Art Garfunkel's "I Believe (When I Fall In Love With You It Will Be Forever.)" My wife and I fell in love to it, had it played at our wedding, and 25+ years later it still works.
But if I can cheat and a couple more, they would be Van Morrison "Tupelo Honey," Buddy Holly "True Love Ways" and Joni Mitchell's "A Case of You" (which in addition to Joni's incredible original version has been covered superbly by both k.d.lang and Diana Krall).
Gotta go, feeling frisky now ... :-)