You'll be able to really learn and experiment advanced functionalities
- on the Tailspin Toys Application (Build definition, Unit Test, and much more...),
- or create your own ones, with reports, new types of WorkItems, ...
It's here : Microsoft® Visual Studio® 2010 and Team Foundation Server® 2010 RTM virtual machine for Microsoft® Virtual PC 2007 SP1
How to use it (and links to download other types of VPC, such as Hyper-V):
By the way, also try the "TFS Integration Platform" from CodePlex to extend the power of TFS outside its traditional usage.
Happy testing... and good luck downloading the 9 Gb !
PS : And for the fun, here is Visual Studio ALM Ranger Projects Scrum Guide.... Personally, I found it interesting but REALLY scary at first sight, despite the fact that I have been using TFS for the last 3 years, with Agile, and recently Scrum for about a year !!