Quite a lot of it's episodic, because linear television was a hell of our own creation. The cold open is usually sufficient backstory. The first few episodes of the original series (sorry, The Original Series) are a little rough, and the first season of Next Generation is reeeal dodgy past the initial two-parter, but both series were jumbled across television for decades. Release order is perfectly fine, and if you skip around, it won't hurt. At least until Deep Space 9 came out as an answer to Babylon 5.

I have one note that applies to fiction in general. A lot of fan-favorite episodes are wildly unrepresentative. That's why they stick out in people's minds. They'll be wacky explorations of familiar characters in an unfamiliar setting, or one character in an amnesia / apocalypse record / It's A Wonderful Life setup, or a wild perspective shift to species that are primitive, pre-contact, or only speak in riddles. These are completely ridiculous excursions from the bulk of the show's story. And they're great fun. But first we ought to appreciate the episodes that capture the premise within the typical stakes of the series. Before the stand-outs can break formula, there has to be a formula, and it's usually strong enough to justify the show's continuing popularity.