A tricky question.

The obvious, and trivially true, answer is that he who does both does more good than either. But that's not what you asked.

So. It can be hard to compare the two options when considering the actions of a single person, since the beneficiaries of the actions do not overlap. Therefore I shall employ a simple heuristic; I shall assume that the option which does the most good when one person does it is also the option that does the most good when everyone does it.

So, the first option; everyone (who can afford it) makes large donations to efficient charities, while everyone avoids those nearby and is unpleasant when forced to deal with someone else directly.

If I make a few assumptions about the effectiveness (and priorities) of the charities and the sum of the donations, I find myself considering a world where everyone is sufficiently fed, clothed, sheltered, medically cared for and educated. However, the fact that everyone is unpleasant to everyone else leads to everyone being grumpy, irritated, and mildly unhappy.

Considering the second option; charitable donations drastically decrease, but everyone is pleasant and helpful to everyone they meet face-to-face. In this possible world, there are people who go hungry, naked, homeless. But probably fewer than in our current world; because everyone they meet will be helpful, aiding if they can in their plight. And because everyone's pleasant and tries to uplift the mood of those they meet, a large majority of people consider themselves happy.