jtspade :
My assumption is theset arrows should point toward each other..?
Probably. As I wrote, the connector is designed to make it physically difficult if not impossible to plug the connector in incorrectly. The painted arrows you mention are nothing more than a clue to help you find the correct position.
If you look at the shape of the holes on the motherboard and PSU connector, you will notice a pattern of complete squares and squares with corners filled (motherboard) or chamfered (connector). These make it impossible to insert the connector in anything but the correct orientation without great force.
Edit: there are two ways you can insert the connector incorrectly without excessive force: by inserting it while being four or eight positions off either way or being off by one row and two or six positions since the connector keying pattern repeats every four positions lengthwise and is the same but offset by two positions on both rows. It is difficult to imagine being that far off by accident and not noticing it.