IF I am replacing a PSU?

I would not; I would unplug the unit from the wall and disconnect each of the power cables from the devices they power and then thread the power cables back through the case so all of them have cleared the holes, channels, and hardware so I could unscrew the PSU and remove it with the cables intact.

If you must cut the wires, make sure the PSU is not plugged into the wall outlet. Know that PSUs have capacitors that will very likely discharge the current they hold as soon as you cut the wires. Wear heavy rubber, or other insulated gloves, or ask an electrician friend to do it.
 

There is release pin on the 24-pin plug. It is located in the center of the coupling, on one side. Locate it, press it towards the wires, and pull the harness straight out of the socket.
 
Do you have an X-acto knife or other thin blade you can use to be sure there is nothing binding the plug to the socket? Find something and insert the blade between the connector and socket - then pull it through each four sides between the connector and the socket. Then try "jiggling" it as you pull on the connector. Be careful, you do not want to pull the pins from the motherboard, if that happens you will have to get a new motherboard.
 

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