"Over the course of the last few months, I have been part of a team working to bring TFS Version Control and MSBuild into my organization. My duties have included everything from process definition to hands-on migration of code from VSS into our TFS repository. An additional (and unwritten) role that I have assumed is to help our developers, QA, and Infrastructure people make the mental transition from the way VSS did things to the way TFS does them. This document was born out of those discussions. I decided to write this up with screenshots from the Version Control Tree Browser project on CodePlex so that it would not have any proprietary corporate information within it. That will allow me to post this for general public consumption without losing my job.
Please feel free to download and use it within your own organizations if you think it is worthwhile...."
Steve has made available a 25 Page PDF where he introduces TFS to the VSS user (Think "TFS Introduction for VSS Users 101").
It's a well written document and one that you should take a look at if your making the VSS to TFS move...