Let $P dx + Q dy$ be a one-form, or if you're using the terminology of an introductory multivariable calculus course, a "vector field" that you can take line integrals of. Then students learn Green's Theorem, which says that if some countour $C$ bounds a region $D$, then $$\int_C P dx + Q dy = \int_D \left(\frac{dQ}{dx}-\frac{dP}{dy}\right) dx dy.$$
From this, one deduces that if the expression on the right hand side vanishes, then the integral around any contour is $0$. In particular, this allows one to define a primitive for $P dx + Q dy$.
Many students (myself included, a long way back) don't pay enough attention to the hypotheses in Green's Theorem and then assume that this is true of the following one-form (or "vector field"), which is my fundamental counterexample:
$$\frac{-ydx}{x^2+y^2} + \frac{xdy}{x^2+y^2}$$
Eventually a student discovers that the integral of this around the origin is $2 \pi$ and then wonders what went wrong. The problem is that the hypothesis of Green's Theorem requires that the form be defined everywhere in $D$.
In other words, this is a fundamental counterexample to the claim that a one-form in the plane with zero curl (where by "curl" I just mean the right hand side of the above) has a primitive.
Furthermore, this is a fundamental example of a nontrivial element in a de Rham cohomology group. In this case, the one-form above generates $H^1_{\text{dR}}(\mathbb{R}^2\setminus {(0,0)},\mathbb{R})$.
