So having checked a couple of spare PC cases there are no resistors in the wiring between the motherboard and the on indicator LED, So I think we can assume that current limiting is done on the motherboard, but you might want to check you specific PC just to be sure.
So you will need to disconnect the existing LED form the mother board and replace it with this circuit using a 4N35 opto isolator.
So when connected if your PC is on you will have a HIGH on the GPIO input and when the PC is off you will have a LOW on the GPIO input.
The 1K resistor is there to protect you GPIO should you accidentally set it as an output.
The 10K resistor is pulling your GPIO input down to ground when your PC is off.