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The gain setting is to fine tune the range of the volume pot e.g. comfortable volume at around 11-1 o'clock. Stick with the standard gain of 8 for normal headphones, there is a good reason why this is the default option. I'd only pick low gain if I was exclusively listening to IEMs and high gain if you only own hard to drive planar headphones. Its more important that you pick the correct impedance (1 or 10 ohm) for your headphones.
I currently have HD650s and plan to add LCD2s and HD800s in coming month. My understanding is that for HD650 which has high impedance, I should stick to 10ohm for good musicality, although 1ohm is more accurate and correct, it's not for long listening sessions because of too much details. I'm right? What about the LCD2s and HD800s?
Stock impedance will be just fine for your headphones. We are really splitting hairs with that. DACmini is just a marvelous DAC and that's most important ;)