Doing multiple things at once in the same computer is complicated. One way of thinking about this is: What would happen if your friend were at your house, with physical access to your computer, and you both tried to use the same computer at once?
Although not necessarily impossible, you'll quickly run into limitations. Trying to connect a second mouse and keyboard will not get recognized as a separate mouse and keyboard by the computer, and the games. Even with controllers, trying to open different games will not work well unless the game lets you assign the specific controller it can and can't use, to avoid conflicts. Some games will not even allow input when they're not the active window.
With that in mind, there are some ways to go about it, with their own drawbacks.
A virtual machine is a separate computer inside your own computer, that can be connected to with Parsec, and used for whatever. Meanwhile, the actual computer is still able to be used without conflicts. Your hardware must be pretty beefy to be split in half while maintaining acceptable performance.
One of the routes you can go is to use James’ Easy-GPU-PV script. It uses GPU Paravirtualization to split one GPU to be used by the actual machine and your virtual machine. However it has issues of its own that you can see in the readme, and in addition, GPU Paravirtualization isn’t particularly a stable feature, so you may not have it work as intended.
If you want to avoid Easy-GPU-PV’s issues, there are other more manual VM setups where you need two graphics cards, so one of them can be completely dedicated to the VM (full gpu passthrough). You'll need to learn how to mess with other VM setups on your own and deal with any issues that may come up by yourself.
Keep both things using a portion of one screen, or, if you have two screens, stream Parsec on one of them and keep things separate across these two screens. Deal with what input goes to what program to allow people to control the correct stuff.
With this you don't need to deal with setting up a virtual machine at all, but you'll depend on scripts built by other users that achieve whatever is necessary for setting up games not made for split-screen, or you'll have to use your creativity to come up with shenanigans.
Here are some useful programs that help with the process. Either scripts that will do things mostly automatically, or programs that let you make your own botched solution.
The main things to keep in mind with or without scripts are: