I recently stumbled on this clip again, after having first seen it on George's blog some time ago. I have to say: Even keeping in mind that any rock star will shed a few personas during the course of their career, it weirds me out to see Neko Case looking young and happy. Because that's not how I like to think of her.
The band is Maow. The year is 1996. The song is "Ms. Lefevre." And the sense of deja vu your feeling probably stems from the fact that you've watched an episode of Smack the Pony.