Barrel heat is particularly an issue with a double rifle, so it is important to fire each barrel once, and then let it cool down. The group would be a group of cold barrel shots.
I shoot off a bench, with a good spotting scope. I put up two aiming marks, one for each barrel. I load 20 rounds (2 of each powder charge, in 0.5 gr increments.)
It may take an hour to fire the 10 2-shot groups. As i fire each shot, I make a note on a pair of target diagrams where the shot went in relation to the aiming mark. When the target is retrieved, I label each hole with the powder charge.
I am looking for loads that shoot to the same point of aim. If I am real lucky, one of the loads will print to the same place.
Then I load a bunch of that load, and shoot a slow 4 shot group (2 each) and adjust the sight to shoot POA.
I found one bullet for my rifle that will do that, with one powder charge. Nothing else came close. But it is a good Barnes bullet and I only need one load.
For plinking and practice i use a much cheaper bullet and just zero one barrel to shoot POA.
If you are unlucky, you will find that a pair of different powder charges are needed to make each barrel shoot POA. That is, you might find that 55 gr in the right barrel and 59 gr in the other shoot to the same place. I have a rifle like that. I mark the case heads with red and green ink and load different ammo for the left and right barrels. The range or game would determine which barrel I shoot first.