I'm going to save you a TON of time here. With the APR K04 V3.2, I've tested everything you're asking about here.
100 Octane:
If you run 100 octane on a 93 file you're pissing away money, you will not make any more timing advance anywhere near the 28-29 degrees I saw on the 100 octane file. What you will see (in data) but not really feel is reaching the full requested timing without any correction factor whatsoever. 93 pump (top tier) gas barely has any correction factor so it's still a waste.
If you run 100 octane file, there are a few things to remember. Sealed 5 gallon drums only, in the ground 100 octane is not the same as a sealed 5 gallon drum with guaranteed fresh fuel. Running your 93 tank to low then filling with a sealed 5 gallon (or more) of 100 octane is not 100 octane, it's diluted. It is recommended to drain all 93 fuel from your gas tank from under the car then fill with 100 octane. Finally, after listening to my first recommendation (sealed gas) and maybe listening to my second recommendation (drain), you will need to drive the car around a bit to let the file adapt, do not go WOT right out of the gate. After you add some around town and highway miles you can start opening it up. The last check is to log correction factor with a 3rd gear pull or 4th gear pull from 2,000rpm to 6,500rpm. If you see 0 correction factor, you're good. If you see -1.5 here and there, I wouldn't be concerned. Any more then you have another underlying issue. I have drained my tank of 93, filled with 5 gallon of 100 octane and drove around on the 93 file for safety, filled another 5 gallon of 100 octane and switched to the 100 octane map and started logging to check for no correction factor.
Methanol:
IMO nothing will beat the addition of methanol. I've run 100 octane, ethanol and methanol. Methanol, when properly placed and dialed in, can bring stock turbo, K04 or BT to life. In terms of hardware, I will always recommend Aquamist. Recently, I've recommended Aquamist jets and their additional hardware with the use of other controllers. The pumps are all the same. The Aquamist jets blow away any other jet in terms of quality, built in check valve, built in filter, spray pattern and atomization. I had successfully dialed in an Aquamist HFS-4 controller with 4 direct port jets and one post intercooler jet (tapped in the APR intercooler outlet) to run 100 octane on a daily basis without any correction factor on 93 pump gas for a year. Others have done it with one large throttle body jet but direct port guarantees a more exact distribution to each cylinder. No reason in risking a cylinder to save money on jets. The post intercooler jet will cool the intake charge which will show the IAT sensor a lower intake temp which will advance timing. When the ECU doesn't see any correction factor as advances timing based on IATs, it can further advance it and you'll have the methanol to drive octane to well over 100 octane. Think 110-115 was the number depending on your water to methanol ratio (I run 80% meth).
Ethanol:
On a 93 file, you will not get over an E25-E35 blend (depending on the ethanol content of the E85 at your local pump) without starting to max out the HPFP/injectors. To properly calculate your targeted blend, you should buy an E85 tester off JEGS or Summit. Test the E85 content at your local pump (winter vs. summer blends), download an E85 mix app to help you calculate ratios, make up a batch, fill your empty tank, clear your fuel trims (disconnect battery or VagCom), drive on 5 gallons. The first mix will be about 5%-10% lower than your calculated target. Fill with another 5 gallons of your ethanol blend, by the second or third fill you'll be at your targeted ethanol blend. You'll need to measure long term fuel trims after this testing to see how much fuel it's adding to compensate for ethanol's additional volume requirement (think less fuel mileage). The car should idle and run smoother, acceleration should feel better as well as you increase ethanol content.
Now, if you want to hit E55, which is where I maxed out the HPFP and injectors, you'll need direct port methanol. Sounds crazy right? Gas, ethanol and methanol? By running direct port methanol and turning up the controller for more methanol volume, it offsets the amount of actual gas needed for combustion. This would show the long term fuel trims pulling fuel, thereby creating a margin with the OEM fuel system. It's this margin that allows you to increase your ethanol content up to E55. You reduce gas by addition of methanol to increase gas when ethanol content is added/increased. The goal is to net it all out.
I'm sure I could add a lot more here but I've been meaning to summarize this for a year now in other threads and I finally found the time....