"Why pushing on a solid mass would cause its thermal agitation to raise?"
It doesn't.: Earth's interior heat ratio between pressure and atomic decay
"why we have higher percentage of radioactive isotopes in the center of Earth rather than in its surface?"
We don't know how exactly radioactive isotopes are distributed in the earth. Radiogenic heat in the core may be insignificant, also because the elements responsible for radiogenic heat are found rather in the Earth's bulk (mantle and eve more so crust) than in the core (Lithophile elements). The core is mainly kept hot by primordial heat, sotosay left over heat from the release of gravitational energy during accretion and differentiation, tidal heating may also have a small part in it. What is the total Earth's interior energy budget?
Mantle and crust store the most of earth's heat and host most of the radioactive isotopes that generate heat, specifically the crust. There's also this reasonable looking Wikipedia article.
The agree to disagree stage is what makes science "science".
Super high pressure at the center of it
It's not the pressure per se that's causing the heat, it was the process of getting to the pressure when the Earth's formed. Compression creates heat. That's easy to know - just touch a bicycle air pump after filling up. There's also the issue of gravitational potential energy converting into heat once Earth was accreted. The the pressure and heat are together the result of Earth's formation. It's not that pressure itself makes the heat.
Radioactive decay
According to what we know, the three modern heat producing elements (thorium, uranium and potassium) are actually concentrated in the mantle, with an even greater concentration in the crust, which is just the top few kilometres. It's still deep for us humans, but extremely shallow when compared to the core. There is still some debate on this (see the two other answers), but my own personal opinion is that it's safe to say there's very little U Th and K in the core.
Also read my very relevant answer on the World Building website: