Grimoire equals EXPERIENCE/Time-Invested at least. Of course, as with anything, skill usually increases with those things. Whether it be a job, dancing, gaming, etc. So when you see someone with a higher Grimoire, it's more likely their skill will/might reflect coming from time and experience. That's really what it comes down to. It doesn't mean they WILL be highly skilled, just more likely.
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Also, I have 4740 Grimoire. Now look at my Crucible k/d. In short, like I said, it more reflects time and experience; not skill in EVERYTHING Destiny.
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There was 2 parts of the thread, a PvE part and a PvP part. Read the whole thing