It's not easy, I can say that much.
A good basis in electrical engineering will help - as will a knowledge of manufacturing processes and capabilities.
As a start though, you could look at a PSU as a set of steps in voltage conversion.
For example;
220/110 V =>12V
12V => 5V
12V => 3.3V
12V => -12V
12V => 5V Standby
plus switching circuitry.
Some very basic info here:
https://en.wikipedia.org/wiki/Power_supply_unit_(computer)
You could probably try playing with power supply modules to get a basic understanding of it all - but don't plug it into any hardware you value till you've tested.
High voltages can be very dangerous, so you take the risk if you want to do such things.