The default isn't overprint — it's knockout: whatever colour sits on top gets its shape "cut out" of the colours beneath it first, and only then prints into that cleared hole. The problem is registration — if the printing plates aren't perfectly aligned, the cut hole and the actual ink land slightly apart, and a sliver of white paper shows through the gap.
Turning on overprint skips the cutout — the top ink prints straight on top of whatever's underneath. Where the two inks overlap they blend slightly, but no misregistration can ever expose white paper. It's most common for black text sitting on a coloured background.
It's not something to flip on everywhere, though — overprinting a light colour on a dark one just muddies or disappears into what's beneath. It's mainly safe for something dense like rich black, where the overlap doesn't visibly change the result.
When to use
Commonly used for black text or logos on a dark background. Keep knockout for a light spot colour on a dark background — overprinting it there just distorts the colour.