I feel like I'm missing something obvious here, but once I've synced my controller to my TV, there's no way I'm ever going to sync the controller again to my PS4 unless I plugged it via mini USB.
I've tried removing the controller from the Dualshock and the Bluetooth menu of the TV. But everytime I press the PS button, it'll sync with the TV instead of the PS4.
If you connect the controller via usb to your ps4 and press the ps button it will now be synced with your ps4, it resets what is was previously synced with.