It depends on your plans for future development. Therefore, 
Regarding the software,
- If that's all you want to do, you can use XLinx software that comes with Keithley's equipment via RS-232 or GPIB (in this case, buy the card from Keithley too)
- If you want flexibility and power with new and difficult projects ahead, LabVIEW is a good choice.
- A cheaper development solution is TestPoint, especially if you are used to Visual Basic programming style.
Regarding the interface,
- RS 232 is the low cost solution.
- If you choose GPIB, it's better to have the card from NI when using LabVIEW (and the one from Keithley when using TestPoint). So, it's important to assure that the card match the software rather than the instrument.
Regarding the OS,
- don't s
pend extra money on other operating system … use what you have, it should be fine
- probably win 98 is a good choice in order to avoid some win95 (age) and NT/2000 (architecture) related problems
Hope this helps