I'm used to simulate only small analog circuit, as references and amplifiers. In your case, ngspice doesn't have a simple function to calculate the ADC linearity. You have to output the transient simulation results to a text file, and then make your measurements using another software. It could be octave, or even python.
Just be sure you have your testbenches working fine. If you're sure your circuit already works for a ramp or sinewave circuit, then, show us your testbench and simulation control structures.