First, back up all data if you haven't already done so. No matter what happens, you should be able to restore your system to the state it was in at the time of that backup.
In the Finder, hold down the option key and select Go > Library from the menu bar (Lion) or otherwise open the Library folder of your home folder (pre-Lion.) From the Library folder, move the entire contents of the subfolder Caches (not the folder itself) to the Trash, then log out and log back in. Empty the Trash. Test.
If the problem is not solved, open the Library folder again and move the entire contents of the subfolder Preferences (not the folder itself) to the Desktop. Log out and log back in. The account will then be pretty much in a clean state. Test. If you can still reproduce the problem, then put the Preferences folder contents back, replacing any that were created in their place, log out, and log in again.
If you can't reproduce the problem in the clean state, then start putting things back in the Preferences folder piecemeal, starting with items that seem unrelated to the issue. I can’t be more specific. After each group of items, repeat the log out/log in cycle and test. At some point, the problem may reappear, in which case you know that something in the last batch of files you restored is at fault. If it never reappears, the problem is solved.
This will be a very time-consuming process, but that’s the best I can do in this setting.