Offset usually happens when you have mismatched devices. So, if you run a regular simulation with all devices ideal, you should not see an offset at the input of the comparator (input-referred offset). So, to know how much offset the comparator has, you have to introduce a mismatch in the devices.
Mismatch is usually done to; Vth, L and beta of the transistor. If you know the values of those paramter that will procude the worst case scenario, you can change your netlist manually and run the same regular transient simulation. This is usually NOT done, because you usually don't know the values that produce the worst case scenario.
The other way is to do it though montecarlo.
For montecarlo, you need to specify how many sigma variation of the above paramters you want the simulator to mismatch them and the simulator will do the rest.
The output of the simulator will be different for different simulators.
To know the input and output format of MC (montecarlo), you need to consult the manual of your simulator.