Read it again, they severed their ties with the federal government - "do ordain and declare that all the laws and ordinances by which the State of Tennessee became a member of the Federal Union of the United States of America are hereby abrogated and annulled." The state government that ratified the Constitution continued to exist.
If the constitution is the supreme law of the land, then it is illegal (though not necessarily immoral) for secession to occur as there is no mechanism for such an action.
Re: all your posturing about the supremacy clause - as has been pointed out - the founders refused to grant the federal government the power to negate state laws. The supremacy clause merely maintains that the Constitution and federal laws "made in pursuance thereof" are the supreme law. Laws not "made in pursuance thereof" are null and void. Unless there is something within the Constitution to indicate that the states granted the federal government the power to hold them captive, the right is a state right - just as the 10th so plainly declares.
People who have that habit of stretching existing language to read as they want it to cannot ever be shown their error. There are several on FR who suffer from that affliction.