Rename the PCLauncher (Example).ini file to just PCLauncher.ini removing the (Example). Now Navigate to your Rocketlauncher Folder, then modules and finally PC Launcher. No need to set a Rom_Path as the location of each gamed is controlled by the method below. Roms you can leave blank as its all controlled in the PCLauncher.ini file.
Open the Emulators.ini file and manually type 'PCLauncher' as your default emulator. (If you don't have this folder you may need to launch RocketLauncher UI Just Once) To do this your RocketLauncher Folder, then Settings and finally PC Games. Then set PCLauncher as the default 'Emulator' in Rocketlauncher for your new PC Games wheel. If you have more than 1 PC Game create a new wheel for your 'PC Games' and make a simple database etc like other wheels.
This is awesome, and makes adding Windows Items like games and media a breeze. With Rocketlauncher there is a module called PCLauncher.