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As a start, I suggest you read through the Expat Arrivals pages on Education and Schools in Spain and Education and Schools in Barcelona.
In terms of your own business, take a look at this useful page on working in Spain for more info on registering your own business.
If you have any more specific questions please ask away.
See Banking and Taxes in Spain for a brief overview.
Basically if you are a resident in Spain (there for more than 183 days of the year) you are liable to pay tax on your international assets and income. BUT it sounds to me like your business will be taxable within the UK as well. So the best thing to do would be to elect to remain a non-resident while living in Spain - in 2010 you could do this, and as far as I know the law hasn't changed. That way you would be taxed in the UK but not in Spain. You would still need to register with the Spanish authorities to do this though, rather than simply npt paying or declaring anything. See: http://www.telegraph.co.uk/finance/personalfinance/offshorefinance/7196252/Offshore-tax-havens-Spain.html
For additional info, I suggest you take a look at this free Expat Arrivals download - Tax info for UK nationals moving abroad.
Hope that helps! The best advice I could give would be not to take the tax laws lightly and consult with your accountant about all the necessary steps and procedures. Tax from abroad can be complicated at the best of times, and Spain is known to have complicated bureaucracy...