On MSDN, there are a series of articles to help explain how to use VSTS and TFS within a large organization.  Called Global Bank: A Scenario for Visual Studio Team System 2008.  This article has an excellent introduction to the possibilities of how VSTS and TFS can assist with your software development life cycle. 

There is a lot I love about VSTS and TFS to help in managing development.  And there is some room for improvement.  The article shows how a company utilize all aspects of VSTS.  For instance there's a good introductory scenario using the architecture tool.  I'm not sold on this tool for various reasons, but if you haven't tried it out, there's a good example of how to use the tool.  What sets this apart is the interconnections between the different tools. 

Another problem I have with the presentation of this is that it follows a more waterfall method.  So I'm thinking an agile scenario might be a good story to create.  Hey that might be a great idea that I might write!  But if you don't have a mature software organization, this series could help you visualize how to grow that organization.