A font can ship two forms of the same letter — say, lowercase "a" as a double-story shape and as a simpler single-story circle — and let a developer pick which one to use. When a project wants a specific letterform (a logotype detail, say) but commissioning a whole new font is overkill, picking a font that already ships a stylistic set for it is a lighter path.
In CSS, `font-feature-settings: "ss01" 1` turns the tag on directly; `@font-feature-values` can name a set so `font-variant-alternates: styleset(yourName)` reads more clearly — at the cost of one extra setup step.
Stylistic set numbers and what they actually change differ per font — one font's `ss01` may change something completely different from another's. Whether this site's system fonts define any stylistic sets at all is something only measurement can answer, not documentation, so the demo actually toggles the tag and measures whether width changes.
When to use
If a brand typeface offers an alternate letterform as a stylistic set, turn it on selectively where that specific shape matters — logos, headlines — not sitewide.