Sure they can. So can ordinary people. Hence the existance of the word "Defy" and "Defiance".
If you are a federal official of any type...even a forest ranger...than you have to obey Presidential executive orders.
If you are a state official...even a state forestry official, then you have to obey the governor’s executive orders.
Beyond that, the two shall never meet. A state official of any type...is not bound by the President’s executive orders...end of the story.
When you look at your local sheriff or city police chief...he’s bound by law (city, county, state, or federal), and that is the limit. Executive orders...are a totally different ballgame, and it’s obvious that news people are the last people on the Earth that you want to get advice from.
What makes the current picture a bit comical is that the President is now telling various federal agencies not to obey the law, and they are carrying out this directive. Why bother even meeting and passing any laws at the federal level...at Congress or the Senate....if they can’t be obeyed?
Yep, States can defy EO’s with nullification and local Sheriff’s answer to their county constituents. I think in the very near future we are going to see a whole lot of nullifyin goin on.