The first emulator you don't go out and get is bleem! It had it's chance, and it failed. Lousy customer support, infrequent updates, and it just didn't work that well. It is now dead and buried. Leave it there.
Next we have Virtual Game Station from Connectix. Oh, wait. Sony bought Connectix, and so there won't be any further updates for this product, either. However, if you do have it, it's not a bad program. It's very easy to set up and has a high compatibility rate. If you happen to be running Windows 2000/XP, don't worry. Sapu released a patch for it here.
Finally, we have ePSXe, which stands for Enhanced Playstation Emulator. That's right, this nifty little program not only lets you play PSX games on your computer, it makes them look better, too.
Rather than give a whole tutorial here, I'm gonna point you to an excellent one already written up. Head on over to Easy EMU and click on the ePSXe tutorial in the left frame. Please take the time to set it up, it really is worth it.