First of all:
EPS12V is an alternative to ATX which is used for high-power systems (e.g. Dual CPU motherboards). An EPS supply uses a 24 pin molex connector to connect to the motherboard. ATX uses a 20 pin connector. Some EPS supplys have an adaptor to convert the EPS connector into ATX. EPS supplies also have the square 4 pin molex connector which supplies 12V to the CPU(s).
PFC (power factor correction) is of dubious relevance to home users. It is irrelevant to European users; PFC has been a legal requirement for PC PSUs for many years - and therefore all EU supplies are PFC. I'll explain very briefly why PFC might be relevant:
A convetional PSU has a low power factor, that means it takes more amps from the mains than you would expect it to. Let's say your pimpin' new PC needs 220W of power - you would expect it to take 2A, but without PFC it may take 3A. It still uses 220 W. However, if you run an office or a server rack, or hold a big LAN party, then the extra amps need to be taken into account, or you'll overload your power strips, or trip circuit breakers. Most electricity suppliers (especially to homes) charge only for the actual energy used (i.e. Watt hours) and ignore the number of amps needed to achieve this. Some suppliers may charge for the amps used, but for domestic use this is uncommon. If you pay for kWh on your bill, then you do not pay for low power factor. If you pay for kVAh then you do.
The +5 or 3.3V supplies could handle the power for the CPU, but there would be problems getting the power to the voltage regulator for the CPU. Supplying a CPU from 5V would require more than 2x the amps needed at 12V - this leads to lower power quality, needs thicker wires from the PSU, better quality connectors, thicker traces on the motherboard, etc.
It's easier to do this with 12V, especially as the ATX spec was not designed for such high currents on the 5V line. I've seen several motherboards (using high-performance CPUs (athlons) powered by 5V) where the 5V pins on the ATX connector have got so hot that the plastic connector had melted.