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If you've ever used an emulator such as ePSXe, you'd know that the .EXE file on the PSX CD is the main executable!

Actually, it's just a little program to get the game loaded. The actual game code is hidden in the disc itself and doesn't get shown as files. :x

Also, I'm interested to know if ...

I've used the Breaker Pro, and it does indeed work. It should allow you to play whatever burned discs you have, including any games you make yourself.

As for doing that, it's as simple as compiling a playstation executable and copying it to a CD!