I'm loving Undaunted's method, though I confess I have never bothered to actively attempt to memorize these pairs. It has happened naturally over the course of flying to a bunch of different airports, though. I have got to tell you that in my experience, getting an adult to do homework (especially if they already have their private license and already know everything about flying) is really, really tough. Even motivated adult students just want to go home and not think about VOR navigation for a while after buzzing around in the soup for two hours.
O.K., so when I'm teaching VOR navigation, there are a few things that must be memorized by my student, or I'm at a loss. They just have to spend 15 minutes REALLY THINKING about this, and it'll become clear.
Rule #1: RADIALS ARE FROM THE VOR (or other navaid).
Rule #2: ALWAYS SET YOUR OBS SO THAT YOU WILL WIND UP FLYING THE TOP, E.G. THE DG AND OBS MUST BE MADE TO LOOK ALIKE ONCE YOU"VE TURNED ONTO THE RADIAL IN QUESTION.
Rule #3: THEREFORE, IF YOU WANT TO GO TO THE VOR, YOU MUST PUT THE RADIAL NUMBER AT THE BOTTOM OF THE OBS, AND IF YOU WANT TO GO AWAY YOU MUST PUT IT AT THE TOP. "From-Top To-Bottom" is a little memory aid that some of my students have glommed onto. Get it? The radial number goes in the top of the OBS if you're going FROM the VOR, and so on.
Getting them to center the needle is on you.
Perhaps the most valuable thing I can suggest is get him the heck out of the airplane and into a simulator (a PCATD will do fine). The stress in the cockpit might be bugging this poor dude out, and he may be confusing the information the OBS is providing him with the information the HI provides. Not that I remember this from the silly things I did during my instument training or anything. So get him into a sim and set him up for some intercepts... show him where he is on the instructor's screen, the direction he's heading, and how that correlates to what his instruments say. Take the heat off, and he may have a breakthrough with minimal effort on your part. I remember getting really dumb really fast under the hood, and all students have these moments. Being able to sip a Coke and press "pause" can make all the difference.
Good luck. I know how painful this lesson can be.