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I've taken over a collection of models, some of them a bit poorly assembled.. Is there a good way to dissolve plastic glue.? I seem to remember that it sort of welds the plastic..

There's nothing to dissolve, plastic 'glue' is a misnomer it's not an adhesive but a solvent.

Polystyrene Cement works by slightly melting the surfaces it is applied to and when those surfaces are pressed together the melted surfaces reharden as the solvent evaporates leaving one solid piece of plastic.

The only way to break apart a miniature assembled with poly cement is with either a knife or a hobby/jeweler's saw.

If plastic cement was used very sparingly, you might be able to file off / putty up a bit of "cement rash" from some parts, but since plastic cement works like welding, you cannot really remove it, the bonds & forms it creates are permanent once it has fully cured

Your only option is to cut them apart.
Maybe re-melt the gap with more poly cement, if that isn't going to melt the detail off the model.