E = mc^2 is the rest energy of an object. It has energy even at rest. It's the energy you'd get if you converted the mass to energy.
KE is the energy of motion of a moving object, the energy due to the motion.
In relativity, one expression for total energy of a mass is E = gamma * mc^2 where gamma is the relativistic factor = 1/sqrt(1 - (v/c)^2). This is equal to 1 when v = 0, and it grows toward infinity as v approaches the speed of light.
So in relativity, KE is the difference between the total energy of a moving particle and its rest energy.
KE = (gamma - 1)*mc^2.
In classical physics, KE = (1/2)mv^2.
You can prove that when v is not close to the speed of light, say 10% or less of c, then (1/2)mv^2 is a good approximation to (gamma - 1)*mc^2.