The biggest issue with adding a second CPU to a dual CPU system after the fact is that the CPU's may not technically be a matched pair. Much like Operating Systems that get patched after release CPU's also go through multiple revisions and updates over time, everything from the stepping (the actual version of the CPU Die) to the microcode running in the CPU.
Using a tool like CPU Z can help you identify the stepping among with other details of the CPU you currently use, which can also help you find a second CPU of the same type. Otherwise when you perform your upgrade, you'll need to keep a look out for system instability, random crashes, etc.
With respect to the BIOS, most systems can automatically detect a second CPU's presence and adjust automatically, some do require you to enable multi-cpu support in the BIOS. This isn't tricky and usually requires finding the right setting a quick look up online for your motherboard manual will give you everything you need!
Bear in mind as well that software licensing may be an issue if you are running Windows Server Standard I believe that's licensed for up to 8 cores out of the box (I cant remember) but you may need to purchase additional license packages for additional extra CPU cores over the base license. For Windows 10 you might need to upgrade to Windows 10 Pro for Workstations to unlock improved feature support for this type of configuration.