Team Build in 2008 is completely revamped from what was provided in 2005. I am assuming that you are talking about 2008, since it is the more current version.
A great place to start is over at Buck Hodge's blog. Buck is the team lead for Team Build. Specifically, he has an article called TFS 2008: A basic guide to Team Build 2008 which is a great starting point.
Also, as a person working on a team migrating to Team Foundation Server, I highly recommend training with a Microsoft-endorsed training provider. We went with Notion Solutions. It is inexpensive and fairly reasonable quality. It is self-paced video training with hosted labs, and instructor question and answer time available, if needed.