Line to line is testing the two sides of a 220 single phase circuit to see that the voltage is as expected. Line to neutral is looking at the voltage between one side and the neutral wire to see that the voltage is as expected. It can show if neutral isn’t connected correctly and is “floating” rather than being essentially a ground.
Just measuring the voltage. Line to ground and line to neutral should both return the voltage. Neutral to ground should return 0. Just a way to make sure the outlet (or whatever) is wired correctly. It doesn’t actuality prove neutral and ground are correct, they could be swapped, but neutral and ground being swapped are very unlikely to cause any dangerous problems.
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