Not unless they're using arms. Unquestionably they're opposing lawful federal authority.
Nullification is one of the contentious points in the US context, particularly since it featured in the run-up to the US Civil War. It's why you might see some people trying to draw a line from the Confederacy (or school segregationists in the '50s) to opponents of immigration enforcement by ICE.
Somewhere before civil war it's possible to cross the threshold for "insurrection", and trigger uses of the Insurrection Act. What is "insurrection" is not defined by the constitution. If "obstruction to the laws" meets whatever other characteristics are customarily required, use of means up to and including the regular forces is authorized.