I'd have a look at some searches and evaluate the competition, then use a tool like WordTracker to see what search volume is like on these keywords. I'd then pick a list of 2/3 to start with, and go back to any of several tools to find related keywords. I then start with quite specific keyphrases early on. For example, say I eventually wanted to target the keyword "gadgets". This is a big ask for a new site, so I'd start with more specific phrases like "USB computer gadgets", "battery powered gadgets", "gadgets for children" etc etc. Come up with a list of specific phrases, then have a look back at your search volume tool and see what that's like, to narrow it down to 3/4 keyphrases to initially target.
I'd then work hard at optimising for these, and only once I've established myself in the rankings for these would I move on to more specific keywords. Maybe next I'd try "USB gadgets" or "computer gadgets". Then finally once you're establised for these, go full out for the "gadgets" keyword.
Probably I'd pick 2/3 "end-stage" specific keywords, then get general keyphrases related to each of these, and work through the steps for each of the end stage keywords.
SEO is a long haul - you have to be prepared to work up from the bottom.
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