Can't find the VSTS window or feature you're looking for under the View menu? There are options sprinkled all over the menu in VSTS. First of course make sure you have the TFC client installed right (and in the right order - VS and then TFC), or you won't see anything. If you know you have everything installed, and ye olde right click isn't doing it for you, here are some suggestions that might help reduce the amount of time you spend hunting and pecking:
How to connect to Team Foundation Server?
Tools->Connect To Team Foundation Server.. or View->Team Explorer, then click on the icon with the plus sign and the chess pawns.
How to close a bug, issue, work item, etc?
Someone called me on the phone this morning asking how to do this. Edit the "state" dropdown and change it to "closed" (if your project has customized methodology it could be named something else), and then save the bug. There is no icon or menu item that will close the bug for you, this is a property built into the form itself.
How to create a bug, issue, work item, etc?
Right click on Work Items in the Team Explorer and if they set up your methodology template correctly at project creation time there should be an option there that will create a bug. I think I mentioned this before but it may be called something else, if your group calls them "product anomaly reports", defects, issues, etc.)
Creating other random things that are special for VSTS
File->New lots of VSTS widgets have their own file type, be on the lookout for ways to add them that way, or via right click add gestures.
Test->Windows for the following: Test View, Test Manager, Test Results, Code Coverage Results, Test Runs
Source Control (the mother lode of options)
File->Source Control for Unlock, Get Latest Version, Get, Unshelve, Check Out for Edit, Lock, Check In, Resume Conflict Resolution, Shelve Pending Changes, Undo Checkout, View History, Exclude from Source Control, Refresh Status, Compare, Properties, Workspaces, Add Selected Projects to Source Control, Open from Source Control, Add Project from Source Control, Migrate Code Analysis Policy Settings to Solution, Change Source Control
Tools->Performance Tools for the Performance Wizard, and Performance Session (will launch a wizard that helps you kick it off)
Source Control Explorer
For some reason it is always tricky for first-timers to find the Source Control Explorer (previously known as Version Control Explorer) in the UI. I've found two ways: View->Windows->Source Control Explorer, or open Team Explorer with the Team Project active and double click on the last node that's there - Source Control. Bingo.
There are lots of things you do in Team System that create pending checkins in the background because they generate code or add project artifacts - creating a team build type, creating a branch, doing in the designers, creating a new test list, etc. These are local until you check them in, and sometimes you need to bring up the pending checkins window in order to check these in. To get there, go to View->Pending Checkins