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If it's empty, make sure the cache is enabled globally with the Shader Cache Size setting in Nvidia control panel. I've never looked to see if it's possible to disable it on a per program basis, but you might check Oblivion settings in the Nvidia control panel also to be sure you didn't accidentally disable it just for this game.
After all that, deleting Game_Settings.sav in the save games folder should cause it to recompile shaders next time you start the game.
Edit: Also, for me, game started crashing when I set the shader cache larger than default size. Stopped crashing once I set it back to default. YMMV.