PowerVR PCX2 works by passing video output through the bus to the host card. Try to prefer 24/32bit color where possible so it can transfer faster.
The PowerVR's driver provides a tab in the Display Properties that has a checkbox to use the HAL for all Direct3D games. Uncheck this if you want to use your host card or secondary video card (Voodoo) for that. This checkbox only applies to Direct3D. You can also enable it for specific games by adding profiles for games you want to run with the PowerVR card.
Games that use SGL should use the card automatically. Unlike the Direct3D HAL, OpenGL should not detect the card, it can only use the card via using certain MiniGL DLLs with games as the PCX2 does not have an ICD.
I think I76's startup crash is sound related? Try to turn down the sound acceleration in dxdiag and see if that makes a difference. If it were a video card causing the crash, it would occur after "SOMEWHERE IN THE SOUTHWEST..." fades out.
Finally, PowerVR PCX2 only has driver support for Win9x.
Relatively to the Mystique 220 you should be able to see much cleaner 3d image quality, true alpha blending, ordered dithering, and bilinear filtering. You will not see blending functions beyond alpha blending so getting a Voodoo is still a good idea. You can't pair the PCX2 with a Geforce card.