When an old man asked me where the church was, I pointed it out.

Literal

Old-man [by-に] church [possessive-の] location [object-を] asked [passive-れて], I [topic-は] it [object-を] pointed-out.

聞かれて is the passive of 聞く — 'was asked by.' に marks the agent in the passive. 指し示す ('to point out, indicate') is a compound verb: 指す + 示す.