1. "Everybody Here Wants You" by Jeff Buckley
This is one of the first songs from my adult listening life that led me to develop a working theory of Sexy Music. (Much earlier, the first songs that made me feel acutely aware of sex, and thus embarrassed, were "I Want Your Sex" by George Michael -- which still, frankly, shocks me -- and "Darling Nikki" from the Purple Rain album. I also thought "Love Bites" was pretty hot.) Shoot me in advance, but I sort of think this and "Morning Theft" are better than anything on Grace. Or maybe it's not that they're better but just easier, more comfortable, less wrought. I don't mind wroughtness per se but it's not very sexy.
2. "I've Been Thinking" by Handsome Boy Modeling School feat. Cat Power
As above, smoky vocals and that swanky, slanky beat. The lyrics here are also super-sexy -- she's singing about a memory of something that happened in the past (I've been thinking about ... those things we did), rather than about something she wants to do in the future, which seems more dude-style (a la "I Wanna Sex You Up").
3. "Fascination Street" by The Cure
My favorite Cure song. Why is it sexy? Maybe mostly by association; it reminds me of New Orleans and New Orleans is sexy. But also I love when he sings "Cut the conversation, just open your mouth"!
4. "Come to Me" by Bjork
This whole album (Debut) is pretty sexy I think, but this is a particular favorite (and it's pretty-sexy, as opposed to ugly-sexy). Bonus points for strings.
5. "Love or Prison" by Blonde Redhead
Some element of doubt and/or tension is important in Sexy Music. In song, if not in life, I prefer obsession to overconfidence.