The patterns & practices team has just released a new guide aimed at helping you get started using TFS and making the most of it.  This looks to be a really good guide for anyone using TFS, or wanted to see what it can do for that matter. Here's how it's described on the site:

"It starts with the end in mind, but shows you how to incrementally adopt TFS for your organization. It's a collaborative effort between patterns & practices, Team System team members, and industry experts."

You get more info, and download the PDF from http://www.codeplex.com/TFSGuide