I should preface these recommendations with a disclaimer: I've only personally played a handful of these with/against another person, and all but one of those were many years ago. (And two of the three I'm sure about were only played multiplayer in split-screen on a console.)
Nevertheless, I've played all the games by myself to enough of an extent to recommend them (at least conditionally) on that basis, and I've watched multiplayer videos online for a few of the topmost titles.
In roughly the order I would recommend them, with some stream-of-conciousness thoughts about each:
Terraria -- IP-based multi, IIRC; Everyone could play at once (no idea on the upper limit), and it's co-op by default (anyone who wants to participate in PvP has to opt in during gameplay); very much a "wiki game" (i.e., having no tutorial was treated as a feature, not a deficiency), so if no one in the group has played it before, a lot of the convenience features of the interface will have to be discovered or looked up; open-ended sandbox, with enough different things to do that everyone might find something to engross them (or at least keep them busy
Talisman: Digital Edition -- Supports up to 6 players, either on the same PC or online; rather cutthroat (though this can vary, depending on your players); lots of RNG; turn-based (though turns are typically not very long); a single game can potentially take a few hours (though there are setup options to mitigate this somewhat); for online play, only one player needs to own a given expansion for that to be used in the game being set up; there's also usually one expansion available to try for free from the new game setup at any given time (though the base game is fine by itself, and preferable if no one's played before)
Death Road to Canada -- 4-player same-PC co-op; very goofy, despite the zombie apocalypse setting and scavenging-focused survival gameplay; run-based RPM (a.k.a. "roguelite")
Streets of Rogue -- 4-player co-op (I think same-PC and online?); another run-based RPM (mission-based); arguably less zany than
Death Road, but still very light and humorous; tons of options to tailor the game to your tastes (within reason ;P )
Oh...Sir!!! The Insult Simulator -- 2-player head-to-head only (same-PC or online, though); turn-based; an individual match will take less than 15 minutes (I haven't timed it, but I'd guess less than 10); very silly humo(u)r "inspired by" Monty Python (and so requires at least a tolerance for that); might serve as a good palate cleanser between other games/activities
Spelunky -- Has same-PC shared-screen co-op (the normal Adventure mode) and competitive (Deathmatch); even if you find Adventure mode more frustrating than funny, Deathmatch can be great fun (though perhaps only as a palate cleanser between other things)
Barony -- Supports online or LAN co-op for up to 4 players; another run-based RPM (though it's the only one on this list that I could understand someone calling a "rogue-like", since
Barony's a dungeon crawler heavily inspired by
NetHack); first-person & real-time; you can turn off or change some of the nastier mechanics via the options if you find the game too lethal (though it'll still be difficult)
Caveblazers -- I think it's just 2-player same-PC co-op (with dynamic shared/split screen); gameplay's like if
Spelunky were focused on combat, with a side of running up, jumping off of and sliding down walls (unfortunately, neither the fighting nor the platforming/traversal are helped by the somewhat indistinct and thoroughly unimpressive pixel graphics)
JYDGE -- Same-PC co-op only (not sure if it supports more than 2 players); a somewhat nonlinear mission-based twin-stick shooter; the only 10tons game I've played -- some others are probably better for sheer jump-in-and-kill-stuff carnage, and might support more players as well
Unreal Tournament -- LAN or online supported (no clue about the number of players, but, certainly, six won't be a problem for most maps & modes :P ); it's an arena FPS, so skill disparities will really show here
Quake III: Arena -- See what wrote for
UT above: everything there applies here =P
Unreal -- Same deal as
UT, but the multiplayer was a sideshow to the single-player campaign;
UT was an iteration upon the multiplayer from this one, so if you were up for an older arena FPS, there would be little reason to go with this, unless you already had particular experience with/nostalgia for this one
Din's Curse -- An indie "
Diablo [II]-clone" ARPG with IP-based MP & no official cap on players; kinda janky and old-looking, and there's zero story (only sparse tidbits of "lore", and the thinnest of excuses for why you're doing what you're doing); old enough and low-spec enough to run on just about anything, though, unlike
Grim Dawn Epic Pinball: The Complete Collection -- has same-PC multiplayer in only the loosest sense: players take turns playing solo rounds, with play passing to the next (IIRC) every time a ball is lost (probably not counting bonus balls earned through gameplay), with the closest thing to in-game interaction between players being comparing scores once the last ball of the last player's drained (giggity); I haven't played it on GOG (though it's in my library), but from what I remember of the couple tables I played years ago, it probably only supports up to 4 players in this way; might appeal to any oldsters in the group, but I guess the DOSBox-y nature of it might work against the interest of the younger family members