Sample rate != resolution.
I think most mice are already at 400 dpi or something, though the sample rate is normally too low to make it matter (40Hz in Win9x, 60Hz in NT). The normal logitech drivers, at least the v9+ versions, allow sample rate settings as high as 200Hz. You seem to have already used that setting. 100Hz is high enough I think for PS/2 (set it too high, and you are essentially polling the mouse too often and slowing the computer down a bit).
I've seen PS2Rate make my mouse pointer jump in strange ways, so I don't really trust the program to do it correctly. If it weren't an optical mouse, I'd suggest cleaning it.