An analogy might be how if you mix together water and alcohol, you get a solution with less volume than the sum of the volumes. That doesn't mean that there's "negative" volume, just that the volume turns out to be sub-additive due to an interaction of specific characteristics of the liquids. Somehow, some connect sums of particular knots enable possibilities that let it more easily be unknotted.

I spent the better part of the summer during grad school trying to prove additivity of unknotting numbers. (I'll mention that it's sort of a relief to know that the reason I failed to prove it wasn't because I wasn't trying hard enough, but that it was impossible!)

One approach I looked into was to come up with some different analogues of unknotting number, ones that were conceptually related but which might or might not be additive, to at least serve as some partial progress. The general idea is represent an unknotting using a certain kind of surface, which can be more restrictive than a general unknotting, and then maybe that version of unknotting can be proved to be additive. Maybe there's some classification of individual unknotting moves where when you have multiple of them in the same knotting surface, they can cancel out in certain ways (e.g. in the classification of surfaces, you can always transform two projective planes into a torus connect summand, in the presence of a third projective plane).

Connect summing mirror images of knots does have some interesting structure that other connect sums don't have — these are known as ribbon knots. It's possible that this structure is a good way to derive that the unknotting number is 5. I'm not sure that would explain any of the other examples they produced however — this is more speculation on how might someone have discovered this counterexample without a large-scale computer search.