First off, the SMG reset is 2 seconds, not 5, 10, 8 or whatever it is people say. I don't know how the number has evolved so much over the years - the manual clearly states 2 seconds. Second off, this does NOT reset the SMG. It's not a fancy fix-all reset - all it does is calibrate the rollout of the tires so the torque calculations the SMG performs are accurate. You do this reset whenever you get new tires put on the car.
A proper SMG "reset" is really called SMG adaptation and it resets the clutch engagement and shift gate calibration of the car, and must be done with the car hooked up to the proper software. However, this is someone you will want to look into and have the adaptation done when the car is nice and hot and you've gone through the gears. Not with a cold clutch or else everything will be off. If I remember right, doing this also clears out any and all "learning" the SMG has done to get to know you as a driver. The SMG system tries to learn the way you drive so that it drives better with you. It watches how you drives and adapts. Right now, it remembers whoever used to own the car. It has to learn you. (FYI - it has one profile per key, so make sure you are always using the same key, and if someone else frequently drives the car, let them have the other key and let these keys be "assigned" as everything from seat position and radio stations to climate control preferences is also unique to each key).
Lastly, you'll want to have Euro-SMG coding put on your car as soon as you can. Because US-Spec cars had the free maintenance, BMW gave us a different SMG programming that sacrificed shift comfort for clutch preservation to avoid having to install a new clutch. Long story short, it makes the car shift like crap. Once you get the Euro software on there the car will drive much better and you will totally say this is how it should have come from the factory (and it did! - just not in the US lol).
Finally, now that you know all that, I will say that it takes some getting used to (it's a learning curve for both you and the car), and it also helps for you to understand how the SMG works and thus its limitations and your expectations. Right now I'm talking about D mode.
The SMG is NOT an automatic. Automatics have it much easier since everything they do is smooth - why? Because a torque converter has very little back-torque transfer under normal conditions. The SMG is a clutched manual, and thus it has full back-torque transfer so you feel every slip, lurch, and clunk from those clutch engagements. This about how it works - the SMG is basically a guy with a clutch on one foot and a gear shifter in his hand, watch you apple gas and throttle. He looks at engine RPM, throttle input, and current gear to determine what to do. The SMG WILL NOT UPSHIFT unless you are giving it some sort of throttle. You cannot rev it out the 7K, then completely cut throttle and expect it to upshift. It will not do that. I think this is the biggest difference between it and an automatic in terms of programming.
The Drivelogic mode you are in (D1 - D5, or otherwise, D mode, however many bars are lit - NOT the gear indicator to the left of "D" on the instrument cluster) determines the base aggressiveness of the shift program. D1 will will generally be very conservative and shift as early as possible. D5 will try to hold gears and will wait a long time to upshift. You must choose the settings to your driving style. If you are on the autobahn and just slaughtering traffic, D5 might be great - it always downshifts aggressively upon strong throttle application and shifts late and generally shifts quickly. Choose D5 when you're creeping in traffic and you'll want to get out and start kicking the car. In a general sense though, don't use D1 as it starts in 2nd gear and fries your clutch.
My personal preference is D2. I use it in conjunction with P500 (not P500S). D2 shifts relatively early and is smooth, but having it in P500 helps with getting some torque out of the motor. P400 is far too desensitized, in my opinion.
When you eventually get the feel of the car, you'll be able to "tell it to shift" even with D. I now will roll into the throttle and then lift slightly when I want the car to shift. It does so perfectly even in D mode. Also, this means that YOU are still in command of the shift timing of the car even with it in D (you are just using your foot rather than your paddles). I think this is one of the biggest frustrations of SMG, is the car being in the middle of a shift when you need to make a move. This helps alleviate that problem.
Now, for when you are driving in manual mode, by all means feel the car like a manual. Upshift whenever you feel it's the right time. When I drive with this intent the car never gets shifted before 5K, and the car is almost always about 3500RPM. It just feels more alive and ready. Not practical for mileage, no, but I leave it in D to get better mileage. Second, let the car do the work for you. The car will not let you downshift to 1st gear at 80mph on the highway, so if you need max acceleration, just pull the downshift paddle like 10 times and mash your foot once you year the RPMs jump up to the characteristically correct sound. You'll get your acceleration without the BS of having to do quick math to see how many gears you need to go down.
Lastly, and this is really just getting used to the characteristic of an S85, is that the S85 is naturally a high revving motor. It likes to be revved out. In your E39 I'm sure you were used to using that great bottom end and broad mid range to leisurely pull the car everywhere - the S85 is not like that. The S85 wants you to use its rev range. That is where its power comes from. From 3K+ the car wakes up from 6K+ the car just enters rabies mode and all hell breaks loose in the best way possible.
I know this was a long post but I hope it helps you get to know your SMG better. Personally, I love the SMG and think it's an amazing transmission that helps you get the most out of the S85. When the SMG is working correctly, it's amazing how smooth it can be, and at the same time, how brutal it can be in S6 when you're going through the gears.