Visual Studio Team SystemI routinely send customers a list of online resources for them to do some self-learning.  Below is a list of great places to start if you're starting to get involved with Visual Studio Team System, including Team Foundation Server. 

There are many, many other links which I can give you if you want to go deeper in certain areas, so please don't consider this a blanket list.  These items are the more commonly requested resources from new customers of mine.

Visual Studio Team System

Team Suite

Team Foundation Server

Architect Edition

Developer Edition

Test Edition

Database Edition