You will probably glean most information regarding the syllabus and testing requirements, both theory and flying from JAR-FCL1 at http://www.jaa.nl. For an official document it is not that arduous to go through.
There is a AOPA book which also describes the PPL flying syllabus. This might be useful as a secondary reference and is usually available from pilot stores.
On the issue of a question bank. The CAA has its own set of questions not drawn for a central question bank.
Bristol groundschool do something similar on http://atponline.gs but for ATPL and http://www.aviationexam.com/. Both were able to cobble together most of the core questions because they obtained the JAA central question bank and so had a head start.
You would not have this head start and would find yourself having to ask a to of students to feedback questions they saw in their exam before you could even begin to offer a viable product.
From there you will want to maintain currrency and be able to track withdrawn and introduced exams questions. As Dean said, an undertaking 😮
You could clean up if you did something for PPL exams online a la Bristol but it is not something that will pay off straightaway. Bristol are charging £50 for 90 days. You may also find people will buy the cheaper book format PPL Confuser instead, however with an accurate database, they may think otherwise.
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