Gene Wolfe

I've decided to start checking him out, after reading raves about him from pretty much every good author ever. I'd like to start off with his best work. Would that be The Book of the New Sun or The Wizard Knight, or what?

Probably The Book of the New Sun and one of his short story collections like The Island of Doctor Death and Other Stories and Other Stories.

I would suggest either New Sun or his Soldier books.