I had the same sort of problem when I was trying to change the location of the session files. It seemed as if my computer was caching the php.ini file.
The way I solved this was to restart the computer itself, but im presuming you've already done that many, many time.
I know it may seem like a silly idea, but could it be a bug of php or win95? I know its not the most stable of platforms anyway, so could that be why its not working?