We have no instructions on how to break the board.The TPS65217C is designed to power the board from either of these sources, whichever one come first. If 5V is connected it switches to 5VDC when connected.
One way to do what you want is to remove the power connection in your cable, cut the wire. However, if you do that, the processor will not recognize the USB as being connected and will not enumerate.
On power off, the TPS65217C clears all the registers, so any registers that are set, will be reset on power up.
Gerald