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So, I recently acquired some Forge World resin second hand, mostly nice conddition and unpainted, but it's not posed as I'd like, any tips for removing it?

Thanks in advance...

Freeze it.
Repeatedly if needed. Superglue bonds weaken considerably when frozen and thawed repeatedly.

As for solvents for superglue - there are risks involved.
Acetone is the main reliable superglue remover.
It has ONE very bad side-effect on resin, though.
It WILL SOFTEN IT OR TURN IT INTO GOO.

MEK is the other good solvent for it - it turns plastics into goo as well as resins (and it explodes, gives you cancer and isn't particularly pleasant to smell).

Thanks!

Should I work on the joints when it's frozen, or one it thaws?

Once it thaws. Also why I recommended multiple cycles.

When superglues cure, they trap water molecules inside the bond. When you freeze it, the water expands - the superglue doesn't. This weakens the bond by pushing ice crystals into the fracture zones.
Do a couple of freeze/thaw cycles (overnight freezing for best results) - don't try to rush it.