I can't claim to be exhaustively familiar with any of the members of the Obama team outside of the big names most of us are familiar with. Unfortunately, a lot of Obama's choices have been either seemingly politically motivated (Clinton/Richardson) or just downright dumb (Geithner/Holder).
From what I've been reading, though, I think one of the more welcomed appointments is Arne Duncan as Education Secretary. Sure, there was that grammatical error made during his introductory remarks -- then again I'm sure there are several in this post -- but what I like about the man is his genuine support for charter schools. The pros and cons of charter schools have been debated all over so I won't go in to why this is a good thing. Perhaps even more importantly though, Duncan has under his belt the major accomplishment of having implemented a system similar to San Francisco's "weighted-student formula under which kids can take their education dollars to any school - public or private" and includes extra weighted funds for students with additional needs like special education, poverty, and English as a second language. These strike me as progressive and non-partisan solutions to restoring the lustre to our nation's most important national resource.
-- Danish Aziz