Know your gun! Measure the barrel; slug and measure with micrometers. Slug or use pin gauges for the cylinder throats, and measure with micrometers. Calipers have small flats on the edges of the jaws so getting a measurement with the inside radius of the cylinder throat may not be accurate, and may flex in use. As Dufus mentioned on very rare occasions a barrel's groove diameter may be larger than the cylinder throats, but it's still best to make sure. Besides getting dimensions, slugging can show restrictions (Many Rugers are "tight" at the barrel/frame junction) or bulges (big "spots").
I size all my cast bullets to the same diameter as the cylinder throats. Doin' it for years and it eliminates most leading...
Update; I've been seeing some discussions on bullet sizing in the last couple weeks. I guess I'm in the minority on this subject, I like to know all I can about my guns, the important dimensions, and I use micrometers capable of .0005" and measure. It seems many reloaders would rather guess at bullet diameter to gun fit rather than know accurately the diameters of the barrels and bullets. I guess that's OK for them, it's their guns, their ammo, and their time...