C# desktop application on express edition. Worked then didn't work 5 seconds later.
I tried the following.
Start debugging, as soon as you've arrived at a breakpoint or used
Debug > Break All, use
Debug > Windows > Modules. You'll see a list of all the assemblies that are loaded into the process. Locate the one you want to get debug info for. Right-click it and select Symbol Load Information. You'll get a dialog that lists all the directories where it looked for the .pdb file for the assembly. Verify that list against the actual .pdb location. Make sure it doesn't find an old one.
In normal projects, the assembly and its .pdb file should always have been copied by the IDE into the same folder as your .exe. The bin\Debug folder of your project. Make sure you remove one from the GAC if you've been playing with it.