I've already linked to this in the past but as Jeff Beehler notes, the word doesn't seem to have got out loud enough. The full 496 page PDF document provides guidance on how to setup, maintain and use TFS, and is available from CodePlex here. The full content is also available on MSDN. The guide also covers TFS2008 which is coming soon.
BTW Pinched straight from the TFS guide, here is a really helpful diagram of what TFS provides. You'll notice that Version Control is only a small part of the TFS feature set: