Try loading debug symbols manually and see what it says:
To display the Modules window in break mode or in run mod
On the Debug menu, choose Windows, and then click Modules.
By default, the Modules window sorts modules by load order. However,
you can choose to sort by any column.
In the Modules window, you can see which modules have debugging
symbols loaded. This information appears in the Symbol Status column.
If the status says Skipped loading Cannot find or open the PDB file,
or Loading disabled by include/exclude setting, you can direct the
debugger to download symbols from the Microsoft public symbol servers
or to load symbols from a symbol directory on your computer. For more
information, see How to: Use a Symbol Server and How to: Specify
Symbol Locations and Loading Behavior.
To load symbols manually
In the Modules window, right-click a module for which symbols have not
loaded.
Point to Load Symbols From and then click Microsoft Symbol Servers or
Symbol Path.
copied from MSDN
You can also try to delete Visual Studio cache just to be sure (from command prompt):
del /Q %LOCALAPPDATA%\Microsoft\WebsiteCache
del /Q %LOCALAPPDATA%\Temp\VWDWebCache
del /Q %LOCALAPPDATA%\Microsoft\Team Foundation\1.0\Cache