Single-rail puts all 12V load on a single rail. Multi-rail has multiple rails so it splits up the load over multiple 12V rails.
Single-rail
Diagram: http://www.thermaltakeusa.com/ProductHtml/image/W0319RU/outputTable.jpg
To calculate the theoretical number of watts on the 12V rail for single-rail:
$$P_{ 12V }=VI\\ P_{ 12V }=(12V)(69A)\\ P_{ 12V }=828\quad watts$$
So as you can see, even though it is a 850 watt PSU, it can only do up to 828 watts on the 12V rail.
Multi-rail
Diagram:
http://www.legitreviews.com/images/reviews/348/ocz700_label.jpg
To calculate the theoretical number of watts on the 12V rail for multi-rail:
$$P_{ 12V }=V{ I }_{ 1 }+V{ I }_{ 2 }+V{ I }_{ 3 }+V{ I }_{ 4 }\\ P_{ 12V }=(12V)(18A)+(12V)(18A)+(12V)(18A)+(12V)(18A)\\ P_{ 12V }=864\quad watts$$
In the chart, however, it says that the maximum combined power for all 4 12V rails is 680 watts. The actual 12V wattage of 680 watts is lower than the theoretical 12V wattage of 864 watts because this PSU can't do full load on all four rails all at once. Once again, even though it is a 700 watt PSU, it can only do 680 watts on 12V. Both single-rail PSUs and multi-rail PSUs (assuming the PSUs are decent) have actual 12V wattage on their charts (in contrast to relying on calculated theoreticals).
Kutt said:
Which is better for high-end systems? Single or multi-rail?
The reason why single-rail is better is because it doesn't matter how you wire up your computer - you're guaranteed to get the power on the diagram. If you have 16 12V wires on a single-rail PSU, all 12V wires hook up to the same rail. However, if you have 16 12V wires on a 4-rail PSU, then 4 12V wires go to each rail. If you hook up your computer using all 4 wires that come from the same rail in a multi-rail PSU, then you might end up overloading the rail because each rail can only do a fraction of the combined rails. Example: the single-rail PSU given as an example earlier can do up to 69A on its only rail. However, the multi-rail PSU can only do up to 18A only any given rail.
Assuming that both conditions below are satisfied, then both single-rail and multi-rail PSUs offer the same performance on 12V:
(i) the multi-rail PSU is hooked up properly.
(ii) both PSUs over the same watts on the 12V rail.