The muzzleloading hunter battery -- here's one way to look at it. 

The only non-variable of bullet construction and one that is very important is the cross sectional area of a bullet.  If we pick the most sold conventional bullet diameter of all, by far it would the 22 caliber with a cross sectional area .0394".  If we double that we get a cross sectional area of .788 we land closest to the 8mm (.323 a very popular European caliber) and between the .30 caliber (the most popular American caliber) and the .338 Winchester (a popular large game rifle).  Maybe its no coincidence that these have been popular calibers for many decades!  Taking this one step further and again doubling the cross sectional area to 1.576 we are at the 45 caliber pistol (.451-.452) rounds that have become the most popular muzzleloading bullets.  Fueling this is the constant improvements of the .451-.452 bullet diameter to the growing popularity of the 454 Casull, the 460 Smith and Wesson, and now the 450 Bushmaster.

So let's translate this into calibers available for modern muzzleloading.  What we find is that we have to bump up the diameter levels up a notch.  So we go from 22 to 32 for small game, from 32 to 50 caliber muzzleloading with 45 caliber.  However, the shotgun is pretty much the same as conventional shotguns.  

Small game, plinking, and target shooting The .22 Rimfire The closest to this is the 32 caliber.  For small game a 32 caliber round ball weighs approximately the same as a 22 bullet. However the larger diameter causes a lot of meat damage to squirrels so its best as a head shot option if the accuracy is there.

Of course, squirrels can be hunted with muzzleloading shotgun loads also, its just not as challenging.
Varmints and predators up to the size of coyotes 22 Centerfire Again, the closest to this is the 32 caliber. 32 caliber bullets can be found that will shoot flatter than a round ball with energy levels of 22 magnum and up to the smaller centerfires.

The 36 caliber might be an option for larger varmints and predators.
Larger predators, deer, elk, and smaller bears 30, 8mm and 338 Centerfires Here we bump up to the 50/45 caliber. 

There's not much reason to bump up any here unless you are forced to hunt big game such as elk or moose with limited bullet weight.  This is the case in some states so I'd be inclined to move up to a 54 for those states.  If beasts that bite back can be encountered where bullet weight is limited I'd go up to a 58 or 62 caliber to get more bullet weight and live with less distance.
NOTE:  45 caliber muzzleloaders using 40 caliber bullets are not catching on with hunters and becoming less and less available.
NOTE:  The 12 guage can be loaded with slugs and hunted with at shorter ranges also.
Hogs, elk, moose, nasty beasts 45 Centerfire
Turkey, Upland, Small Game, Varmints, Etc. The 12 Guage Shotgun Here's one place the muzzleloading hunter has an advantage over conventional shotguns, loads can be developed specific to the gun and the game hunted without spending a fortune on ammo.  The only disadvantage is being limited to one or two shots.  Many states restrict magazines to three shots anyway for most hunting so not much is given up there.

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