I think you get a complete picture of the Prokhorov metric $\pi$ by combining what Dirk has pointed out and what we already know about the total variation metric. Essentially, $\pi$ is a measure-theoretic analogue of the Hausdorff metric, but loosened up modulo the total variation metric. I will explain what I mean by this.
Suppose we have a probability measure $\mu$. We can imagine two different types (I will call them Type I, Type II) of ways of of slightly changing the measure $\mu$. To make exposition simple, let's suppose $\mu$ is just a pile of N point masses, i.e., $$\mu = \frac1N \sum_{i=1}^N \delta_{x_i}$$ where $x_1, x_2, \cdots, x_N$ are $N$ points in space and $\delta_x$ denotes the point mass at $x$, i.e., the Dirac measure. A type I change is when you cut out a tiny chunk of $\mu$ and then move that chunk arbitrarily. To be precise, we will say that the new probability measure $\nu$ is obtained by a type I change from $\mu$ within $\epsilon >0$ if we have $y_1, \cdots, y_N$ (another list of N points) such that $$\nu := \frac1N \sum_{i=1}^N \delta_{y_i}$$ and
$$ \#\{1 \le i \le N: x_i \ne y_i \} \le \epsilon N $$
An essential property of the total variation metric $\delta(\mu, \nu)$ (between probability measures) is that it allows changes of type I. In other words, we have a constant C such that $\delta(\mu, \nu) \le C \epsilon$ whenever $\nu$ is obtained from $\mu$ by type I change within $\epsilon$.
A type II change is when you move all or some of the particles within small distance individually. To be precise, the definition for type II change replaces the condition
$$ \#\{1 \le i \le N: x_i \ne y_i \} \le \epsilon N $$
with this condition
$$ d(x_i, y_i) < \epsilon \ \forall 1 \le i \le N $$
The Hausdorff metric allows changes of type II in the following sense: there is a constant C such that whenever $x_1, \cdots, x_n$ and $y_1, \cdots, y_n$ are two lists of $N$ points in space such that the above condition holds, the Hausdorff distance between the two sets $\{x_i : 1 \le i \le N\}, \{y_i : 1 \le i \le N\}$ is $\le C\epsilon$.
The Prokhorov metric $\pi$ allows both type I and type II. In fact, you should be able to prove the following fact.
$$ \#\{1 \le i \le N: d(x_i, y_i) \ge \epsilon_2 \} \le \epsilon_1 N \implies \nu(A) \le \mu(A^{\epsilon_2}) + \epsilon_1 \ \forall A$$
This is just a type I change within $\epsilon_1$ followed by a type II change within $\epsilon_2$.
So the Prokhorov metric is simply what you would have come up with if you tried to define a metric $\pi$ with the nice property that $\pi(\mu, \nu) \le \epsilon$ whenever $\nu$ is obtained by moving particles in a $1-\epsilon$ portion of a ``pile of dirt of unit mass'' $\mu$ in any way within distance $\epsilon$ and the rest $\epsilon$ portion of $\mu$ arbitrarily.
Of course we can think of another metric $\pi'$ that satisfies this nice property simply by definition.
$$ \pi'(\mu, \nu) := \inf_{\gamma \in \Gamma(\mu, \nu)} \kappa(\gamma) $$
where $\Gamma(\mu,\nu)$ means the set of all couplings between $\mu, \nu$ and
$$ \kappa(\gamma) := \inf\{ \epsilon: \gamma\{ (x,y): d(x, y) > \epsilon \} < \epsilon \} $$
The nice property of the Prokhorov metric can then be re-expressed as $\pi \le \pi'$ since $\Gamma(\mu,\nu)$ can be thought of as the collection of all possible ways of moving the pile of dirt $\mu$ into the new pile of dirt $\nu$. Less obvious is the fact that the other inequality $\pi \ge \pi'$ also holds. So in the end, these aren't really two metrics $\pi$ and $\pi'$, they are one same metric $\pi = \pi'$.
The Prokhorov metric reduces to the total variation metric when the discrete metric is assigned to the space $M$. So another way of thinking of $\pi$ is that it is a generalization of the total variation metric that takes the topology of the space into account.