This was the final official 32X release, and coming out in 1996, I think there are two assumptions that can be safely made about it. The first is that it coming out was something of an adherence to the lost cause fallacy: possibly the publisher specifically had a license to make Marvel games only for the 32X, and they were going to do it whether it made sense or not. The second assumption is that it probably sold incredibly poorly, which is backed up by its modern day rarity and insane resale value.
Is it good, though? Not really. It's not terrible, either, though. Like most Spider-Man games of the time, it's a 2D platformer, you climb and swing acorss the stages, and the boss fights are against existing Marvel villains. Unlike some similar Spidey games, it does have a few stages that are designed in such a way as to allow you to freely web-swing over large swathes of the stage at your leisure. In fact, these stages are so long, that it'd probably take an absurdly long time to get across them on foot. Unfortunately, there's also a few stages that fall into the usual Spidey-traps, like being a long corridor with a surprisingly low ceiling, or being a bunch of enclosed boxes with small entrances and exits.
The plot concerns a plot by Hydra, who have set up a big laser net over New York (the eponymous Web of Fire), and are holding the city to ransom, plus they've kidnapped Daredevil and put him in a birdcage for some reason. After you rescue Daredevil, you can summon him to throw sticks at your enemies! So each stage ends with you fighting a villain in Hydra's employ, and destroying a laser generator, until you get to the Hydra airship/submarine/base stages. The bosses are probably the most interesting part of the game, to be honest, as the roster's made up of some absurdly little-known jobbers. People like The Eel, Thermite, Tangle, and others.
Web of Fire is a game you mgiht want to look into out of curiosity: its rarity, status as the final 32X game, and weird villain roster are all points of interest (and what drew me into playing it). But if none of those things interest you, there's nothing else in the game that will, either. I played it way past the point of enjoyment to get screenshots, but there's no reason for anyone else to do that. And definitely no reason for anyone to pay £500+ for a real copy!