There's two issues:
1) Being a shorter overall caliber, accuracy goes down because the bullet accelerates some distance down the cylinder with no rifling. Also known as the "freebore" effect. Not too significant for plinking, informal practice, etc.
2) Much more serious is the far smaller rim on the .32ACP. It *does* have some rim, which is why this works at all. But if the gun is a swing-out cylinder DA with an ejector star, the rim can get hung up under the star.
The solution is to poke the rounds out from the front of the cylinder with a cleaning rod or similar, and not use the ejector star.
This is a non-issue on SA revolvers such as the Ruger Single Six, because that's exactly how the ejector works - one round at a time, forced out by a rod down the inside of the shell. If NAA ever made a scaled-up SA minirevolver in .32Mag like we've been begging, it would also have no problem with .32ACP.