I don’t think it would spoil anything. They were meant to be viewed in syndication which means people could see any combination of eps in any order. However for whatever reason they were constantly fighting against the format and making netflix shows before nextfix. Like there is an ?8?-part episode IIRC. If you just drop in on that, it’ll be confusing.

As a general thing I think these are widely-understood as some of the standout eps

• In the Pale Moonlight - About having to make difficult decisions in war. Scheming and bending ethics.

• Far Beyond the Stars - A time travel afro futurism episode where Sisko lives the life of a Black science fiction writer in 1950s US. He remembers DS9 reality mostly as a story he is writing — of himself and a future for humanity. But it seems realer than a story. He is considered insane.

• Rejoined - A species who switch bodies every so often are generally prohibited from getting back with their past lovers once they’ve moved on. But these 2 do so anyway and now one of them is a woman so it’s also gay. Or is it?? I think it’s an allegory to lgbt things which just happens to use women tongue kissing. (In the world of the TV show, the scandal is that they are breaking the rule about getting together post-body switch.)

And looking at the list (I don’t know what eps are called so having a hard time knowing what’s what

• Series Premier - I think it was a fun start and set up some conflicts

• House of Quark - Ferengi is forced to marry a sexy klingon lady due to palace intrigue and manages to bring honor to double entry accounting.

• Hippocratic Oath - The enemy in a war for everything has genetically engineered super soldiers that are kept disciplined by an innate drug addiction. Should do-gooder-wanna-be Dr Bashir help them to break the addiction? Will they become chill?

Any epsiodes with the Maquis are good bets (anti0federation, anti-cardassian rebels). There are a lot of bajorian ones about getting shit back together after decades of occupation. But there are lots of one-offs too. Like the one where oBrien goes to mind jail.