Let me try.
Say for instance your peak boost is 14lbs (like your example) and you reach full boost at 3500RPMs... Now you notice at 5375 that your very rich (10.37 when your target was 11.07)... Right away, you think "hey I'll adjust the cells at 5000 and 5500 around the 14lbs row to take care of my richness. BUT WAIT! the car was actually between 10.20 and 10.40 for the entire time I was at full boost. SO instead of adjusting those few VE cells, you can actually go to the column on the left (the comp VE column) and adjust the cell that corresponds to 14lbs (full boost). The column is there for convenience. It makes tuning at particular vacuum/pressure levels easier for you to dial in across the entire RPM range.
The first car I tuned on Jackal (a few years ago), I never even used this column. Now that I'm a bit wiser, I use this column for the first pull or two, then begin adjusting individual cells.
Hope this helps. I could probably do a write-up if need be.