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I found this very good http://www.amazon.co.uk/Understanding-Exposure-3rd-Photographs-Camera/dp/0817439390/ if you're looking for a gouide to taking pictures and what the different settings do. It's not specific to the best way to use that DSLR though.
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I'd meet / invite someone over for dinner that knows his shit and is able to explain the fundamentals of SLR photography.
Beyond that read the manual to get a grip on that specific camera's ways / were to set certain things, but again - I'd always prefer to meet with someone rather than read books.
Other half has just bought a DSLR (700D), is there a decent book/guide I could her so she can get the most out of it?