Dixie Gunworks catalog says the little Remington Pocket Pistol barrel has .326 diameter grooves and .315 diameter chambers. They also say the bore is .310 diameter.
The chamber walls look thick enough to stand reaming out the front of them without making them too thin. Especially if the enlarged diameter is only going 3/8 of an inch or so deep.
While reaming the chambers should improve the guns accuracy, it probably isn't worth the time, cost and effort.
IMO, these little guns are too small to get a good grip on them, the distance between the front and rear sight notch is too short and they are too light to make good target shooting guns.
They are great for plinking and could do a pretty good job at self defense which is what the original guns were made for.
Also, if the chambers are reamed to the larger size there are no standard sized balls that will work in the gun.
From what I see, the next size up is a .350 which would be too large.
Even a #00 buckshot's .340 diameter would be too large IMO.
That said, should nikke ream out his cylinder? Only he can answer that question.
By the way: Welcome to the Forum Nikke.