The Roman
scutum does not really need to be angled to deflect missiles; it's half an inch thick and curved to fit around the body.
http://legvi.tripod.com/id112.html
At longer ranges (100m or more) it would deflect missiles, including musket balls, very nicely. At short ranges the musket balls will penetrate, but then you're only going to get one shot before the Romans are on top of you.
And that is just what would happen; the Romans aren't going to bother with waiting for the musketeers to fire before charging in. That is not the Roman way. They will charge in, take the enemy's volley, answer with one of their own, then close in with their
gladii to finish the job. Once they do the matter is already decided.
And that's a frontal assault over open ground, which gives the musketeers their best chance. If the Romans can approach from cover, or attack from the flank or rear, the result will be even more in their favor.
So how do you defend against the Romans?
Option one: Prepared defenses. If the Romans can't get across your ditch or over your wall they can't close in and the battle becomes a firefight in which your musketeers have the advantage.
Option two: Cavalry, preferably heavily armed and armored. The Romans cannot just charge straight in if there is a force of cavalry waiting to attack their flank or rear once they are engaged; they will have to deal with the cavalry first, which gives the musketeers more time to do their work.
Option three: Field artillery; lots of field artillery. With canister/grapeshot. Attacking over open ground against that would decimate the Romans before they got close enough to engage. They would have to maneuver to approach from cover or from a direction not covered by the artillery, which again gives the musketeers time to do their work.