It does work, but it has drawback....
And I don't think it was used at all, or only rarely back in the cap and ball days. If swapping the cylinders were common, it would be a much more featured item in both the real and fictional histories.
Having and using a second gun was much, much more common, and much more likely.
The historical accounts indicate that, other than a very small number of "experts" (like Hickok) "two gun" gunslingers carried and used the second one as a fast reload, instead of both at once.
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All else being equal (and it almost never is) bigger bullets tend to work better.
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