Before the steady state
One step, computed twice
A step response from the poles is exact. The same step walked forward in time is not, and the difference between them is the trapezoidal rule's own error rather than anything about the circuit. It falls by a factor of four every time the step is halved, which is a claim about a method and can be watched.
Where the behaviour is written down
Two numbers in the complex plane contain everything a second-order circuit will ever do. Their distance from the origin is the natural frequency, the cosine of their angle is the damping — and the fastest-settling circuit is not the critically damped one, which is the case the textbooks name.
The step that is too big
A linear circuit scales — double the input and the output doubles, exactly. A real amplifier does not, because its output can only move at a fixed rate, and the amplitude at which the two stop agreeing is about eighty millivolts for an ordinary part. No transfer function contains that number, because no transfer function can.