Standard printing (4-colour "process" printing) overlaps tiny halftone dots of cyan, magenta, yellow and black so the eye blends them into one colour. Zoom in and it's really just a field of dots.
A spot colour instead uses one ink that's pre-mixed to be that exact colour — a solid, uniform film rather than a pattern of dots. That gives stronger, more consistent colour, and it's the only way to print colours CMYK can't reach at all, like fluorescents or metallics. The tradeoff: each spot colour needs its own mixed ink, adding a print pass (and cost) per colour.
It's mainly used where "always the exact same colour" matters, like a brand logo. Left: dots of process ink overlapping to fake a colour. Right: one solid spot ink laid down flat.
When to use
Use for brand logos or packaging where even a slight colour shift is unacceptable, or when you need a colour CMYK physically can't mix, like fluorescent, gold, or silver. Not a fit for photos with thousands of colours.