Yup, always, always treat it with respect. It depends -- you might get away with it, it might bubble loosely (if vigorously) and just splatter a bit, or material with trapped moisture might bubble and hiss as the vapor is let out through pores or whatever. Or it might explode on contact, or a moment later. There's no guarantee, whether it will or won't; the potential for a steam explosion is always present, but neither is it guaranteed. While "it depends", you can't know what factors it depends on (could be surface pores, chemical adsorption, spooky stuff like that). And you certainly aren't going to take note of such things on that one occasion when you're working in a hurry, or not really paying attention. So, the usual safety stuff: if you make a mistake, and get away with it -- don't beat yourself up over it, but do take a moment to be mindful of what you've done, or not done, and what to do in the future to prevent it.
And yup, any other mitigation is welcome. PPE, cotton, wool, leather or fireproof clothing; loose so as not to trap anything that might fall in, or to take it off quickly if necessary. Gloves, long sleeves: probably not a big deal, I'd probably avoid gloves on account of reduced dexterity and risk of trapping splatter, while sleeves I'd go either way on I suppose -- the tricky thing with solder, versus hotter metals like bronze or even steel (as in welding and foundry contexts), is it can stick in place (even without gooey-melty poly clothing inbetween), kinda maybe as often as it rolls/bounces off. For which sleeves would give you some protection (and you can do the shimmy-shake if something slides up your sleeve, it'll leave a mark but nothing too threatening), but it might be worth the comfort (say in a hot workshop) or mobility without.
And yup, for burns, having something nearby to cool your skin (and anything potentially stuck on it) can save you -- not from burns at all, you have to administer water within seconds to do that -- but reducing the burn severity by a whole degree or so, is a heck of an improvement by itself.
Mind how fast different parts of skin will burn: I tagged myself the other day trying to juggle a hot air machine; ended up just brushing the nozzle, with the thin skin on my forearm just below the wrist. It was probably a second in contact by the time I felt it, and that was probably enough to do the damage; it was another second by the time I realized what happened, and one more by the time I got my tongue on it to try and cool it down. (If you don't have water to hand, your mouth is always moist!) So, a futile effort in that case. I have however saved my fingers from burns a few times, using this protocol -- when I can react to it (I'm usually seeing what my fingers are doing!) and because finger skin is a bit thicker. So, this is just a tiny optimization really; it certainly won't save you from the consequences of a blow out, for example.
And obviously, be careful with that supply of water, don't get careless and splash it on the solder pot itself.

There exists, I suspect, a certain optimal distance, between liquid solder and liquid water, which improves health without potentially worsening outcomes.

Anyways...
Last pot I used, either came with, or was mounted to, a stainless steel saucer of sorts (I forget what exactly, it was a while ago). Partly this just gathered a bunch of crap that people skimmed off the pool / knocked off things being soldered; but also it serves to catch spills, whether intentional (as above) or not.
I suppose something with an inward curled rim would be ideal, so even if it tips over 90°+ it contains most of the spill, that would be cool. No idea if you'll find those around, or what, just neat if so...
Placement. If you have the space in a workshop: a clear table, maybe with some signs denoting the hazard, would be good. Have the power cord up on the table, plugged into a mounted or overhead outlet so it's not a trip hazard? And if it's out in the open, ventilation probably isn't a big deal, maybe a fan to just dilute things ("the solution to pollution is dilution"!). If in a smaller setting, like a lab: yeah, a fume extractor, fume hood or exhaust fan would be welcome.
Work surface should be clean and, needless to say, non-explosive. Wood typically chars and smokes, and may pop a bit but I think is unlikely to cause dangerous splatter, at least unless it's the kind that's really prone to popping (pine?), or wet. Laminates tend to char and blister, I don't think they're prone to popping or splatter, but maybe not preferable. Laying down a sheet of metal, or anything refractory (fiberglass mat/felt/fabric/board, suitable stone/cement/ceramic materials) should do. (Mind that generic concrete tends to spall when heated, as do most rocks. Something that's been heat treated already, or at least known to be reliably porous, should be good. I bet a soapstone work surface would be really fancy... if pricey.

) If nothing else, a layer of fine sand is very porous, reasonable insulation, and will support spilled metal until it cools. (The enterprise-grade solution for foundries, no less!)
Also, like, don't simmer it for ages. Turn it on when required, and turn it off when you're done. If you forget you have more stuff to do, well, better waiting a few more tens of minutes than forgetting to turn it off. Plan to prepare your work beforehand, then do everything at once. Simple, responsible stuff like that.
Tim