Her right of entry as a spouse was given to her before Poland joined the EU (May 2004) under British immigration law. That would have been for 2 years in the first instance. She could then apply (still under British domestic law) for indefinite leave to remain on the grounds of being a spouse (= settled status). I don't think that anything described in the terms you state has anything much to do with residence permits in EU law - it would be the same for anybody given leave to enter for settlement on the grounds of marriage to a British resident who has indefinite leave or the right of abode.
Problems only arise if the marriage breaks down within the 2 year period. In domestic law once someone has indefinite leave to remain/settled status it would be unusual for it to be withdrawn (I don't say impossible), though it would be lost if she left the UK for a period of 2 years or more.
This looks like one of those cases where the fact that she is now an EU national obscures the fact that her rights have been determined under British domestic law. EU law cannot derogate from rights arising independently under national law.
A person with indefinite leave to remain is not a person from abroad and not subject to immigration control unless the leave has the express "no recourse to public funds" condition. It would say on the certificate / letter giving her indefinite leave if that condition was attached, and it would be unusual for a spouse.
She should have no legal difficulty in claiming benefits on the back of her right to reside, but if she does my guess would be that DWP will get hung up on the fact she is now an EU national. They are always not good at recognising other forms of rights of residence, and may have to appeal to get it sorted out.
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