VSTS resources on MSDN
MOC Curriculum: Course 2631A Optimizing the Software Development Lifecycle with Microsoft Visual Studio Team System
VSTS walkthrough
https://msdn.microsoft.com/vstudio/tour/vs2005_guided_tour/default.htm
Useful blogs:
James Manning https://blogs.msdn.com/jmanning/
Rob Carron https://blogs.msdn.com/robcaron/
Richard Murillo https://blogs.msdn.com/rimuri/
Buck Hodges https://blogs.msdn.com/buckh
VSTS Blog https://blogs.msdn.com/vstsue/
Team Foundation https://blogs.msdn.com/team_foundation
MS Build https://blogs.msdn.com/msbuild/
VSTS Quality Tools https://blogs.msdn.com/VSTSQualityTools
Team System FAQ https://msdn.microsoft.com/vstudio/teamsystem/support/faqs/foundation_techfaq
VSTS Architecture:
https://blogs.msdn.com/robcaron/archive/2005/04/15/408426.aspx
https://blogs.msdn.com/rimuri/archive/2006/04/26/584403.aspx
https://msdn2.microsoft.com/en-us/library/ms181233.aspx
https://msdn2.microsoft.com/en-us/library/ms400658.aspx
Overviews:
VSTS Source Control: https://msdn2.microsoft.com/en-us/ms181237.aspx
Team foundation build: https://msdn2.microsoft.com/en-us/ms181710.aspx
Team project portal: https://msdn2.microsoft.com/en-us/library/ms242883.aspx
MSF for agile: https://msdn.microsoft.com/vstudio/teamsystem/msf/msfagile/
MSF for CMMI: https://msdn.microsoft.com/vstudio/teamsystem/msf/msfcmmi/
VS Team edition for architects: https://msdn2.microsoft.com/en-us/library/57b85fsc.aspx
VS Team edition for developers: https://msdn2.microsoft.com/en-us/library/47f7hz7y.aspx
VS Team edition for testers: https://msdn2.microsoft.com/en-us/library/ms182409.aspx
VS for DB Professionals: https://msdn.microsoft.com/vstudio/teamsystem/products/dbpro/