This Constitution, and the Laws of the United States which shall be made in Pursuance thereof; and all Treaties made, or which shall be made, under the Authority of the United States, shall be the supreme Law of the Land; and the Judges in every State shall be bound thereby, any Thing in the Constitution or Laws of any State to the Contrary notwithstanding.

That section that I emphasized is what absolutely and unequivocally destroys all arguments that misuse that clause.  The Founding Fathers made it very clear that the Supremacy Clause trumps neither the Enumerated Powers nor State Sovereignty . . . period.  Properly understood, as you have pointed out, the Constitution always trumps federal decision-making.

Abuses of the Supremacy Clause began with Reconstruction, and have continued to this day.