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I am looking at trying to start drilling my gun barrels is it better to wait till after they are painted or before they are printed.

Before painting. You want a fine sharp hobby knife or scalpel. Place this in the centre of the barrel and turn a few times to create a pilot hole. Then take your pin vise drill and appropriate bit and drill the hole, taking care to be gentle and not remove too much but leave an even hole.

Yes, before painting. It's part of the modelling, so it makes sense to do it before priming.
I personally find it easier to use an awl to create the indentation needed to center the drill properly. I find it quite difficult to center the hole using a hobby knife. I don't know if it's because it's shiny or asymmetrical, but I often lend offset with those.

Before...

CB

Always before. Pin vice and a 1mm drill bit work well on something like a bolter.

My technique is covered in this tutorial. Works pretty well.

https://www.winterdyne.co.uk/maz/winterdyne_tutorial1.pdf

Before painting. It lets you rebuild if you overdo it (like I often do).

I do both ways. The holes are easy enough to cover with some touch up paints.