Let's say only one socket has a processor in it, and you have four modules. If you put the modules into both the blue and white slots of two channels, the memory will run in dual-channel mode. If you put them all into the blue slots, they'll run in quad-channel mode, with twice the memory bandwidth.
Again, all the memory channels run in parallel.
If you have two processor sockets populated, and there's not enough memory modules to use all four channels on both processors, it's more important that each processor has an equal amount of memory, so you'll want two modules for each processor socket, with the modules in the first two channels of each socket.
@dustytrash Good question. You can do that, but that extra memory will not have the higher memory bandwidth of the rest of the memory on the system because it doesn't have matching memory in the other channels to run in parallel with.
It'll work, but not all of the memory will be accessible at the same level of bandwidth.
Remember that the memory in each channel runs in parallel. If you have one channel with two 16 GB modules and the other three channels with one 16 GB module each, you'll have 80 GB of memory total, but only the 16 GB that's common to all the channels will actually run in parallel. The extra 16 GB in the first channel will be on its own.
If you have six modules, filling two channels with 2x16GB and two with 1x16GB, the 16 GB that's common to all channels will run quad-channel, while the extra 16 GB in two of the four channels will run dual-channel.
That all assumes it's all with one processor socket. If you have six 16 GB modules and two sockets with processors installed, fill the first (blue) slot of three of the four channels of each socket. This will give each processor 48 GB in three channels.
Think of each memory channel as a lane of traffic through which the processor and memory communicate. The processor can communicate with all lanes simultaneously. Two memory modules that share a lane can't go any faster than a single module on that lane, but modules on separate lanes can communicate with the processor simultaneously.
Each "lane" is a blue-white slot pair. This means that if you put four modules into two pairs of blue and white slots, they're sharing two lanes of traffic. If your processor's "memory highway" has four "lanes", you'd obviously want the memory to be on all four of those lanes rather than be limited by the speed of two.
This is only complicated because you have a dual-socket server with four memory channels for each socket, and two memory slots for each channel. Most PCs only have one processor socket and two memory channels, each of which may accept one or two modules.
On a typical desktop, it's little more than "install memory in equal pairs".