No, the PS/2 protocol is not at all like RS-232, other than the fact that, yeah, it's a serial protocol.
What brand of USBRS-232 cable were you using? Although most of them seem OK these days, in years past there were some notoriously flaky ones. I think we still have a Belkin brand unit kicking around at work here that wouldn't work with AVR Studio, for instance.
That being said, a PCMCIA serial port card is a "real" serial port in that even software (such as DOS programs) that directly access the hardware I/O registers will work with it. If you can find one inexpensively on eBay (etc.), it's a good investment.