Calhoun was not a libertarian in the current sense; but he was a very observant and influential political theoretician. His best work was A Disquisition on Government. It argues that the best governments require the largest consent within the branches and levels of government, and gives historical examples illustrating his concept of concurrent majorities. This means the requirement of wide agreement before the government can act. Nullification was seen as just one sort of limit on rule by overweening majorities. One of Calhouns examples was Poland, in which for a time laws had to be approved unanimously by the legislature, which (he asserted) led to Polands most prosperous times, and built a habit of compromise and toleration of minority views.
I regard Calhouns concurrent majority principle as extremely valuable. As he pointed out, it is (or was) embodied in the U. S. Constitution by the requirement that laws must be approved by more than one branch of the government; and by the division of powers which formerly separated federal and states rights. The states Calhoun saw as having a right to dissent from laws which they judged were unconstitutional. The only other alternatives would be tyranny or war, both of which we have experienced.
Nullification infuriates ideologues, for it seems so messy. But the alternatives are despotism, or bloodshed. Which is preferable?
If a state were to dissent from the outrageous and clearly indefensible Roe v. Wade decision, who would actually be harmed?
Concurrent majorities is an excellent and practical freedom principle.
Of course, we are way beyond the point in our history where rights are actually observed by reference to the Constitution. State rights have been abolished by judicial interpretation, and new (previously unimaginable and bizarre) rights are almost daily propounded by ideologically motived judges. This is part of the progressive collapse of our civilization, and shows no sign of abatement.
The ultimate act of nullification would be secession, but that did not work out for the South. Now almost everyone accepts the idea that no people should ever be able to leave a country, except in most other parts of the world.
Stopping the behemoth of dictatorial government is perhaps no longer possible for our society. People accept tyranny because the think that peace requires it. But note that there is no such thing as a peaceful dictatorship. Dictatorships may be quiet, but not peaceful.