To fix spoolsv.exe application error, you will have to remove these files from the system. To do this, perform the following steps on your Windows XP computer:

1. Open Control Panel, select Performance and Maintenance, select Administrative Tools and then select the Services option.
2. In the Services management console, locate the Spooler services, right-click on it and select Stop.
3. Next, open the C:\Windows\System32\Spool\Printers folder. (Here, we are assuming that your Windows is installed in the default C:\Windows folder)
4. Delete all the .SHD and SPL files from this folder.
5. Next, open the TMP folder and delete all old and unused files from this folder.
6. Finally, restart the Spooler service from the Services management console.

Note: If you are unable to delete the files in Normal Mode, then you may have to restart your computer in Safe Mode to delete the files. To start your PC in Safe Mode, press F8 at system restart and then select the Safe Mode option from Windows Advanced Options Menu