It depends on your motherboard's memory controller.
If you have a 2 channel memory controller, then the most efficient configuration will be two modules of equal sized ram.
If you have a 4 channel memory controller, then the most efficient configuration would be four equal sized ram sticks.
But the difference is not large should you not have the most optimum configuration.
CPU operation is focused on memory in the L1 cache. Having more L1, L2, and L3 cache will make the biggest difference to memory intensive computing. Even if there is a cache miss, it will only take a matter of nanoseconds to address the RAM modules.
Overclocked, perfectly matched memory can add a few frames per second to a game (like Battlefield for example) and I would expect a similar incremental improvement with your emulators. But it won't make a large difference.
Just packing as much ram into your system as you can afford will have a bigger impact than worrying about 2 or 4 modules.