Hi Waterboy!
First, to get a student´s visa you only have to 1st enroll in a university and pay their big-fees to participate in their $tudy-abroad program.
Next, your then-wife will NOT be able to apply for a work visa unless she has already been offered a job by a specific company for a specific job. This is particularly difficult and nearly impossible. She could most likely go to Spain as your spouse in some capacity, tagging along with you on your student visa (assuming she won´t be a student) but then won´t legally be able to work.
So really, in short, if your wife isn´t offered a job by a Spanish company BEFORE arriving in Spain she won´t be able to get a work visa. And you should start looking for study abroad programs now and prepare to pay. You won´t be able to work either while there so imagine the two of you there on only your savings for a year. Yikes.
Best of luck to you. Saludos, MadridMan
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