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similarly to what happens if you fire .38 Special in a .357 Magnum Revolver, a ring of carbon can form in the cylinder just ahead of the case which will prevent .357 from fully fitting all the way into the cylinder.
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Actually, the issue with 38 Specials in 357 Magnum chambers is not that the ammo will not fit into the chamber, it's that once fired it won't extract. That ridge of carbon where the end of the 38 Special case is slightly smaller than the chamber diameter, so it locks the longer 357 Magnum case in place once it is fired. Unfired, you can put 357s into that chamber and take them out no problem.