I'm not very familiar with Napoleonic battles, but it seems to me that if heavy cavalry was tactically useful at all, I have a hard time seeing it not being useful against skirmishers. In many respects, the factors that make a wavering line vulnerable to cavalry -- lack of dense, coherent formation, inability to present a bayonet wall -- are inherent to skirmishers. Skirmishers seem like a pre-broken line to me.
If heavy cavalry was ineffectual against skirmishers, it seems like this would be because increasing firepower was rendering cavalry tactically obsolete in general, not because cavalry was useful against line infantry while being weak against skirmishers. (If heavy cavalry was generally nearing obsolescence, then line infantry was too, since without the threat of cavalry, lines as a whole just got people shot faster, leading to a sort of "all skirmisher + artillery" army from the mid-19th century until the arrival of tanks and aircraft.)
As I said, I'm not very familiar with the details of Napoleonic battles, so I'd welcome any corrections.