You have a thermostat in the tank, or a thermometer? A thermostat controls heating devices, a thermometer measures temperatures. I don't know of any thermostats that should be in the tank, but I think you mean to say you have a thermometer and hygrometer?
If you are measuring ambient air temps, 85-90 during the day is too hot, you want it around 80-85 ambient air, 82 cool side substrate temp, 92 warm side substrate temp (this is where the BPs belly touches). You will need a probe or IR thermometer to measure this accurately.
What is this homemade humidifier consist of? 50% should be alright, but during sheds you'll need to bump it up to 70% or so.
Head tucked into a tight ball means he is scared and stressed. That is their defense mechanism from predators, and is why they are called ball pythons. They roll up real tight and protect their head. A new BP may do this when touched or bothered, but should un-ball if left alone for a bit. If he is doing this for extended periods something may be wrong. Is the setup in a high traffic area? are you in his enclosure fussing with things or trying to handle too often? If he is left alone he should un-ball and go coil in the hide.
Since you got him 5 days ago he should be settling in pretty quick and not be as stressed. Try leaving him alone for awhile (1-2 weeks), no contact except quick visual inspections and mandatory water changes and cleanings.
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