I think people tend to read too much into things without really evaluating a situation thoroughly enough.
If a person knew they were about to be involved in a fight, or was about to commit a crime, rustling, bank/train robbery, etc…, it would make sense for them to loaded for bear. Since individuals like the James/Younger gang were guerillas in the war, they were accustomed to having several arms on their person because they did most of their fighting from the back of a horse and reloading would not be that easy in such a frantic/hazardous situation. They wore guns of all types all over themselves and their mounts. Logic would seem to say these men knew they were about to do battle they would be well armed and ready to use everything they had or was available to get the job done.
Now hanging out with the family, picking up some supplies in town, or taking in a local barn dance, or scoping out a job, the need to be inconspicuous would pretty much dictate that the less threatening the individual was the better.
Particularly in the days of percussion revolvers, a man who was expecting a fight carried all the shooters he could. Jesse James preferred S&W revolvers during the cartridge era, because--he said--they fit his 'small, aristocratic' hands better. They were also a lot easier to load on the run than Colts or Remingtons.