Here's a post from another site that may be of some help:
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Q. When I switch on my PC every time I get this message and I have to close down my PC to restart it. The message reads - "spool32 has caused an error in spool32.exe. spool 32 will now close. If you continue to experience problems, try restarting your computer."
A. Spool32.exe is a program for Windows 9X, which handles background printing. Using this feature, the print and resume facility is being enabled and enable returning to the program, without waiting for the last page to get printed. However, there are some situations, when this service may give some errors, like anti-virus programs or another utilities causing a conflict with the spooler, use of third party printing software like Hewlett-Packard Port Monitor or Epson Spooler, print spooling utilising Enhanced Metafile (EMF) format (versus the RAW format), printer drivers may have a coding error, terminate-and-stay-resident (TSR) programs or other programs that prevent the Spool32.exe program from running when Windows '95 or Windows '98 starts. Since your problem occurs at the time of starting the computer, it is most likely that either the anti-virus program is causing some conflict in your system or any TSR program is preventing the Spool32.exe to run. In this case, the best solution would be to start windows under step-by-step confirmation. This can be done by pressing and holding down F8 key, when the Windows is booted and hold it till the time you get the booting options like normal mode, safe mode and step-by-step confirmation. Choose step-by-step confirmation and hunt down the program, which is causing this problem. Once you know the program, either uninstall it or reinstall it fresh. I am sure this will solve your problem.
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