a) Yes it is perfectly safe to use two separate power supplies. The only problem you may have is if you power on your Amiga too soon and it your hard drives might not spin up quickly enough.
b) If you power the Amiga through the floppy connector from the PC PSU, then it will power on when the PC PSU is powered on. Be aware though that certain parts of the Amiga won't work without the -12v supply from its normal power connector. Certain parts of Paula won't work, amongst other things. A better option would be to take the 12v, 5v and -12v lines from the ATX connector on the ATX PSU and connect them to the Amiga's standard power socket. That way you have one PSU, everything powers on at the same time, and everything on the Amiga will work.
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moto