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firewire and usb are used primarily for hooking external peripherals into your computer, like a external hard drive, or a flash key, or a digital camera.
PCI is a bus inside your computer for hooking expansion cards in. If you are buying a sound card, PCI is your only option (unless you are looking at an OLD school ISA card, or somebody finally developed a PCI-express card). It is possible that this card may have built in ports on the back for usb and firewire, but I wouldn't understand the purpose.
There are pci cards whose only function is to add additional usb and firewire ports, but that has nothing to do with recording audio.
I have heard of external devices that will accept an analog signal from, say a guitar amp, and convert them to a signal useable by a sound card, or maybe even across usb. Not sure on this, though.
What product are you looking at? (link, model number, etc.)
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