In order to pair device you need to open Device Manager. Then in device manager select proper tab and perform pairing as in instructions.
Note that for PS Move, Driver4VR will instruct you to download and install PSMoveService.
Once device is paired you will see it on ‘Devices’ list. Then you need to select Device and Controller and click ‘Assign’.
For VR Gamepad there is no need to assign but instead you need to select Controller and then press ‘Assign buttons’.
Below Devices list there is Preview option that allow visually see orientation of the controller as well as status of buttons.