The thing that catches people out with sterling silver is tarnish. It will go dull and a bit grey if it sits in a drawer unworn, or if it gets splashed with perfume or hairspray, and the first time that happens people assume they've bought something fake. You haven't. It's just what real silver does, and a soft cloth sorts it out in under a minute. Once you know that, it stops being annoying and just becomes part of owning it, the way you'd know not to put a wool jumper in a hot wash.
It's not the right choice for everyone, though. If you swim a lot, or you're the sort of person who forgets to take jewellery off before a shower and then forgets again, you'll be polishing more than wearing. It's also not the one to reach for if you want something completely maintenance free, the kind of earring you put in once and never think about again. There are metals that behave better in that sense, they just don't have the same depth of colour, and to me that's a fair trade, but it's worth being honest with yourself about which one you actually are before you spend the money.
In the shop, check the fastenings properly rather than just looking at the front. Press the butterfly backs or the hook closures between your fingers, because cheap ones feel stiff for about a fortnight and then go loose, and that's how earrings end up lost on a bus. Have a look at the hallmark too if there is one, it should be small and neat, not stamped crooked, which tells you something about how carefully the rest of it was made. And check the weight. Good sterling silver has a bit of heft to it, not heavy exactly, but not weightless either.
Where it struggles is against anything already busy. Gold jewellery worn in the same ear or at the same neckline fights it for attention and neither wins. It also looks slightly wrong against very warm toned fabrics, rust, mustard, that sort of thing, where the coolness of the silver just sits oddly rather than working with the colour. It comes into its own in autumn and winter, against navy, grey, black, deep green, when the whole point is a bit of quiet shine against something muted.
The one mistake is buying it and never wearing it, out of some vague worry about keeping it perfect. Silver that gets worn regularly actually tarnishes less, not more, because the contact with skin keeps it bright.