With 2 rails you can isolate heavy power draw devices from each other, say the video and mobo on one rail and the cpu on the other, so that if you get heavy pull from one device it won't affect the other with fluctuating voltages.
Apparently, 16A + 16A does not = 32A in most cases. You'll have to check the specs for each PSU - when both rails are maxed out, total power output is usually less than 2X a single rail.