As much as a i love Xcode 4, (and i really love it) it swallows errors that symbolicatecrash script spits out. This caused me to send loads of time trying to fix an issue that i knew nothing about.
Well here's the solution.
1. Do a project clean in Xcode (cmd+shift+K)
2. Delete the entire 'PROJECT/build' directory
3. Go to ~/Library/Application Support/iPhone Simulator/VERSION/Applications/UUID and delete each folder that contains your application name. Be sure to do so for each Version of the SDK.
And then attempt to symbolicate your reports.
I'm led to believe that some genius (who i'll target at WWDC and buy him/her a beer) thought it would be a great idea to use Spotlight to find dSYM files. Sadly i don't believe they thought (or could) apply any sort of search order, leading to spotlight returning random binaries. (When good ideas go wrong).
FYI. If your a member of the Xcode Team, i genuinely appreciate all the work that you folks put into 4.x.