Readers in Hawthorne's day (and people in Puritan times) would have understood Pearl's reference to the Black Man not just as someone to be avoided or someone evil, but as a reference to Satan himself. To state, as Peal does, in public that someone was a "Black Man" would have been derogatory; this is why all the adults stand in shocked silence. Out of the mouths of babes!
The term has less to do with skin color as it does to create a division between Puritans and everyone else; they freely applied the term to Native Americans and Africans alike. White skinned Purtains would have thought themselves as God's chosen building a New Jerusalem in the New World; everyone else, but especially non-whites, were evil and associated with the wilderness. So for Pearl to state what she does is to knock Chillingworth from his high social standing in the...
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Purtain community.
We have our archetypal Satan -- hoofed, pointy tail and horns, etc. This is a recent conception; probably in Hawthorne's day (and most definitely in Puritan times) the icon would have been more like the forest god Pan -- a mischief doer who is king of the forest, outside of city culture. For Pearl to state that "he cannot catch little Pearl!" is to underscore that Pearl is the literal embodiment of mischief, born a "wild child."
Functioning more as a symbol than a real character, Pearl of "The Scarlet Letter" works for Hawthorne as both a literal personage and as a figurative one. Often, therefore, she is representative of the feelings of her mother, Hester Prynne. For instance, in Chapter IV Hawthorne narrates that the infant
writhed in convulsions of pain, was a forcible type in its little frame, of the moral agony which Hester Prynne had borne throughout the day.
Acting again as the representative of Hester's feelings, little Pearl expresses Hester's misgivings about Roger Chillingworth in the above passage as well as defining an area of meaning and any interpretation that falls within that area. Earlier in this chapter, for example, Hawthorne writes,
He[Roger Chillingworth] now dug into the poor clergyman's heart, like aminer searching for gold; or, rather, like a sexton delving into a grave, possibly in quest of a jewel that had been buried on the dead man's bosom, but likely to find nothing save mortality and corruption.
Thus, little Pearl's exclamation about Roger Chillingworth provides an interpretation of this earlier statement of Hawthorne; it gives the added meaning that Chillingworth is malevolent, violating the "sanctity of the human heart." Also, when Pearl declares, "But he cannot catch little Pearl," her role as the guiltless product of her parents' passion is also made evident. For, there is nothing in Pearl that Chillingworth can violate or torture.
This quote is from Chapter 10. Obviously, Pearl is speaking to her mother.
She has been looking out the window and has seen Chillingworth talking to Dimmesdale. Chillingworth is trying to dig into Dimmesdale's past. He is suggesting to Dimmesdale that he (Dimmesdale) has dark secrets (which of course he does).
Then Pearl throws a prickly burr at Chillingworth and runs away, shouting the quote you cite. The significance is that she sees what a mean and evil man Chillingworth has become and she can tell that he has his hooks in Dimmesdale.