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It was mentioned in this thread several times that the 4790k and 5820k are the best value for average Pio use.
They are likely the best performance/cost at this point although 5820k is going to be faster, especially if you overclock.
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Is the difference worth it if I'm only going to use Pio for postflop?
That's a question only you can answer. Bare 5820k is going to be around 1.25x faster but you can easily overclock it for additional ~20% which would result in about x1.5x performance. The difference between DDR3 and DDR4 should be negligent (at least it was I benchmarked it some time ago).
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As new things are added to Pio and it is optimized etc. is having the ability to have DDR4 much better? Also, how much do different memory frequencies affect Pio?
I don't know sadly. My best guess is that RAM frequency won't make much difference in the future (but get at least 1600Mhz).
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If I decide to solve preflop spots as well does it then make more sense to get the 4790k build and use the rest of money to get the Edge version (I'm thinking of getting the Pro version first) and rent a server for pre flop like it was mentioned here?
I am a fan of renting instead of investing in own hardware but again it's a very individual decision. With preflop it's a bit more clearcut at you would need to get at least 64GB of RAM and even then you may sometime want to run bigger trees. You may rent something for a few days or a month to do it but building such a computer at home is quite an investment.
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I assume solving pre flop is not an option on 4790k because of the RAM being capped at 32gb.
It isn't at the moment (with the exception of very simple spots in 6max like steal vs BB with one sizing). You can get even 128GB of RAM with 5820k but again, RAM is still very expensive and renting is likely to get cheaper.