I think a better way to go would be to build a clockport adapter for the 500. Consider what kind of devices you'd want to use, and whether clockport devices already exist. If you roll your own, that means writing drivers as well as building hardware. With the exception of graphics cards, I can't think of any I/O cards that really need the speed of a PCI slot.
There are a lot of little modules made for embedded system designers that would be great for classic Amigas. Stuff like network cards with their own tcp/ip stack, usb hosts with their stack, mp3 players and more.