So far I can establish the following, just need some help with the last bit.
Everyone's situation is different. Here is ours:
I am a Uk Citizen who just got married in Brasil to a Brasilian.
We want to go and live in Spain.
I will get my empadronamiento when I arrive in Spain. My wife will enter on 90 visa waiver as she holds a Brasilian passport.
We have already got our marriage certificate and my wifes birth certificate both legalised in Brasilia by the Spanish Consulate.
We take these documents (empadronamiento, marriage cert, her birth cert and both passports) to Oficina de extranjeros in Barcelona and we apply for a residency card for my wife.
Then we wait for the residency card, about 2 months (according to parainmigrantes.info)The question is: how soon can she work, and how does she apply for the work permit?