To emulate CD32 with WinUAE, all you have to do is the same as when emulating the other Amiga systems. You need to make a configuration that suits a CD32 system as well as having the CD32 extended kickstart-ROM file to go with it.
How to set it up properly is explained in the Readme.txt for WinUAE in the "CD32 emulation instructions" section.
Then the only thing you have to do to play a CD32 game is to insert the CD in one of your PCs CD-drives and start the emulation. The CD32 startup-screen should appear; launching the game from the CD.
(recommended to use a joypad for this, mapped accordingly to a real CD32-joypad for best experience;))
But what goes for the kickstart-ROMs I'm afraid I don't provide those, but do some searches in Google and you'll probably find something.