What does an exterior (second) derivative such as in $d^2=0$ have to do with second derivatives as in single- or multi-variable calculus? Is this a correct start:
Calculus derivatives are good for Taylor expansions (and thus optimization), and curvature.
Exterior derivatives are needed for integration -- and are essential for generalizing the Fundamental Theorem of Calculus (i.e., Stokes theorem).
That $d^2 = 0$ is probably something you were already taught in vector calculus.
For instance, you probably remember that $\nabla \times \nabla \phi = 0$ for $\phi$ a scalar field, or that $\nabla \cdot (\nabla \times E) = 0$ for $E$ a vector field. It's a good exercise to show that both of these can be written as $d^2 f = 0$ and $d^2 E = 0$.
Of course, you know that $\nabla$ can be written in terms of partial derivatives:
$$\nabla = (dx) \frac{\partial}{\partial x} + (dy) \frac{\partial}{\partial y} + dz \frac{\partial}{\partial z}$$
You should also know that the above vector calculus identities rely upon the equality of mixed partial derivatives:
$$\nabla \times \nabla f = \frac{\partial^2 f}{\partial x \partial y} dx \times dy + \frac{\partial^2 f}{\partial y \partial x} dy \times dx + \ldots$$
But since $dx \times dy = -dy \times dx$, the equality of mixed partial derivatives reduces this to zero. The logic is similar for the vector field case.