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I used to spray paint my Legos all the time as a kid (so they would match color haha) As I recall, the solvents in some spray paint can slightly dissolve the surface of Lego plastic, but not enough to damage the structure. I would recommend getting a spray specifically designed for plastic such as Rust-Oleum plastic paint and of course, experiment first on a sacrificial Lego. You may have more luck if you slightly sand any smooth surfaces with a light grit paper (high number) to promote adhesion. 

 

Legos are made from acrylonitrile butadiene styrene. Games Workshop models are a polystyrene formula. The acrylon portion of Legos is what makes them much harder than GW models. 

Edited by Astral Arcane

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