Yeah it's more about people interacting in a voluntary manner. The first and probably last rule of libertarian philosophy is that it's not OK to initiate aggression against others. So two individuals entering into a contract is OK but one person threatening another with violence is not.
The fact that the state/government has a monopoly on violence means that your interactions with them aren't necessarily voluntary. Many people don't have a problem with paying for roads, or some semblance of a military, or schools or whatnot.
But the very nature of a state is that if you don't do what it tells you to, you have no recourse. Someone might not put a gun to your head but you have to know that there's no negotiation.
If you perform civil disobedience you can and probably will get arrested. It happens all the time.
Choosing to break an unjust law doesn't mean that a judge will understand the injustice of it and let you go free, nor is there any assurance that jury would acquit you. That's what I mean when I say "there's no negotiation"
Once a police officers decides to arrest you all negotiations have ceased and they may do whatever the law tells them to, or whatever the law lets them get away with, or perhaps a bit more.