My wildest guess is that that the top barrel is more accurate since the sights are mounted to it whereas the bottom barrel is adjusted by bending the barrel relative to the top barrel.
Shoot with the not so accurate bottom barrel first and if you miss, use the accurate top barrel.
That would be a very wild guess, as any and all the double 412's i've owned or shot, both bbls have been equally accurate and that's as accurate or more accurate as the average bolt action rifle.
Anyway, GB is partly right, but the biggest reason to fire the bottom bbl first is, it's the proper regulation order. Meaning that all S&S double rifles are regulated by fireing the right bbl first, and all O/U double rifles are regulated by fireing the bottom bbl first. That's the way they should be regulated and that's the way they should be fired.
DM