from what I've read watts divided by volts=amps so if I have a single 12v rail and a 460watt psu my amps would be 38.3 is this a correct method?
If the power supply has only one output at 12V, then you'll be able to draw around 38A. If this is an ATX power supply then this is not the case, and you'll have to consult the label on the side of it. An ATX PSU rated for 460W is the maximum power available in total for all rails, but individual rails have individual ratings a lot lower than this.
The total output current (amps is a unit!!) and total output power are not the same thing. Look on the side of the PSU. It'll tell you the ratings for each line.