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I'm new to 40k and Kill Team - the games, the fluff, and the construction of teams - so, please excuse my ignorance.

Is it possible to swap in Steel Legion troopers for Cadian Shock Troopers (or Catachan Jungle Fighters) using the stats of the latter? Do some modeling to equip a specialist with a melta or plasma gun rather than the missile/grenade launcher that SL squads typically come equipped with?

I'm asking purely for aesthetic reasons; I like the look of the Steel Legion over Cadians. I think it'd be fun to use them as grunts paired up with some Tempestus Scion, and maybe a sniper in there.

Yup, there's nothing stopping you from using Steel Legion troopers instead of Cadians/Catachans. There's no regimental doctrines in Kill Team and there's no explicit rule saying you need to use the corresponding models with their doctrines as long as you explain beforehand.

Last i recall there are no specific regiments,chapters or anything for kill teams. so you can use whatever imperial guard flavor you want.

Excellent. Thank you for the replies!