Do you have a quote of what Tao is saying? I'd put union and intersection both at a definition level.
You'll always have undefined terms because otherwise you'd get an infinite regression of terms. Then there are defined terms. Axioms typically establish a relationships between terms, both defined and undefined. So I'd put a rough hierarchy as from more fundamental to less, 1) undefined terms, 2)defined terms, 3) axioms. Though I don't think this is rock a rock solid hierarchy.
Consider Euclid's 5 Axioms. He made attempts to define point, line, and plane. A point is "that which has no part". But what does that mean? A line is "that which has no breadth".
Axiom I: A line can be drawn between any two points.
So point and line are not defined there.
Axiom III: Given two points A and B, a circle can be drawn centered at point A through point B.
Again the axiom only has meaning with terms defined before hand.
Axiom V: When two lines m and n cross a third line, l, lines m and n intersect on that side of l where the alternate interior angles add up to less than two right angles.
What's intersection? What are right angles?
But consider the axioms that define the real number system.
The reals are an ordered field having The Least Upper Bound Property having The Rationals as a property subset.
The definition of field relies on notions of sets, elements, and functions by way of binary operations. Ultimately those rely on undefined terms. Without some meaning of sets and elements, none of the axioms make sense. On the other hand, you are not dealing with the real numbers unless you stipulate the Least Upper Bound Property or some equivalent. It's an axiom that's needed as part of the definition of the Reals. So there's basic definitions, then axioms, from which you compose a definition.
Perhaps another difference between a definition and an axiom is definitions are always bidirectional logical statements. Axioms are typically unidirectional logical statements.
Definition: A natural number is even if and only if it is divisible by 2.
Compare this to Euclid's first axiom. While given two points, you can draw a line between them it doesn't necessarily follow all lines have two points. Consequently Hilbert stated this as the third of his postulates of geometry.
Another difference, the negation of a definition doesn't make much sense."A number is not even if and only if it is divisible by two". If we take this to be true, we are radically changing the meaning of "even number".
If any part of a definition fails, you are talking about some other entity.
If any part of a postulate fails, you are typically talking about some other relationship while preserving the meaning of the terms involved. Given a line and a point not on that line with multiple parallel liens going through that point, we negate Euclid's fifth postulate while maintaining the meaning of all terms involved.