You are correct. Unfortunately, state governments don't have a hand in federal taxation. Employers typically withhold the estimated amount from employee's paychecks, and at the beginning of each year everyone submits a tax form. If they paid over their obligation, they get a refund; if they underpaid, they owe money.
Even if someone opts out of tax withholdings, they're responsible for sending their taxes to the federal government each year; typically through a third-party for-profit business (especially now that Republicans trashed the recent IRS pilot which allowed people to file their taxes directly to the federal government for free).
The only solution would be for every resident of that state to individually opt out of federal tax withholdings from their employer, but then they'd be individually liable for submitting their taxes each year. While the IRS doesn't currently have the staffing to handle that if everyone does it, that would require a level of collective trust-in-ones-fellows that simply doesn't exist in this era.
It would be much better if states could offer their protection, but apparently states can't even keep ICE out so the IRS would be no different...
What are they gonna do, build a wall?