I was exploring the inferences drawn from the truth values of $p$, $q$, and $(p \Rightarrow q)$. The truth table of material implication is:
$$\begin{array}{|c|c|c|} \hline p&q&p\Rightarrow q\\ \hline T&T&T\\ T&F&F\\ F&T&T\\ F&F&T\\\hline \end{array}$$
If $(p \Rightarrow q)$ is true and $p$ is true, we can see from the table that $q$ is true. This rule of inference is called modus ponens.
If $(p \Rightarrow q)$ is true and $q$ is false, we can see from the table that $p$ is false. This rule of inference is called modus tollens.
If $(p \Rightarrow q)$ is true and $p$ is false, we can see from the table that $q$ is undecidable. Saying that $q$ is false would amount to the fallacy called "denying the antecedent".
If $(p \Rightarrow q)$ is true and $q$ is true, we can see from the table that $p$ is undecidable. Saying that $p$ is true would amount to the fallacy called "affirming the consequent".
My question:
How does propositional logic deal with the case when $(p \Rightarrow q)$ is false? From the table above, we could immediately infer that $p$ is true and $q$ is false. Is there a name for this "rule"? Does it have any applicability? What within propositional logic would formally prevent one from applying this "rule"?

It is indeed true the falsehood of $p \to q$ implies $p$ is true and $q$ is false. In other words, it is indeed true $\neg (p \to q)$ imples $p \wedge \neg q$. You have presented a semantic proof of a valid argument form that doesn't have a name (that I'm aware of). This should not be suprising because there are many, many valid argument forms that can be constructed in a given system.
From a syntactic point of view, every natural deduction system has a "starting" set of inference rules that contains the primitive inference rules of the system, which you can think of as inference rules we simply take for granted to be true. You can use the primitive inference rules to derive other inference rules, but derived inference rules do not allow you to prove anything new that you could not prove apart from the primitive rules. This is because anything proven with a derived rule can be proven by applying some sequence of primitive rules.
For example, suppose a system defined Modus Ponens (MP), Conjunction Introduction ($\wedge$I), and Reductio ad Absurdum (RAA) as primitive rules. Then, one could derive Modus Tollens $p \to q, \neg q \vdash \neg p$ as follows
$ \begin{array}{llll} \{1\} & 1. & p \to q & \text{premise} \\ \{2\} & 2. & \neg q & \text{premise} \\ \{3\} & 3. & p & \text{Assumption for RAA} \\ \{1,3\} & 4. & q & \text{1,3 MP} \\ \{1,2,3\} & 5. & q \wedge \neg q & \text{2,4 $\wedge$I} \\ \{1,2\} & 6. & \neg p & \text{3,5 RAA} & \square \\ \end{array} $
Thus, in such a system Modus Tollens is a derived rule, proven by the primitive rules MP, $\wedge$I, and RAA.
So, if we wish, we could take the valid form of inference you mentioned
$\neg (p \to q) \vdash p \wedge \neg q$
and give it a name like "toliveira's rule," but in most natural deduction systems (that I'm aware of) this would be one of many derived inference rules that do not have a name. Some derived inference rules are given names because they are used often, provide useful shortcuts in proofs, or capture our intuition well; others are more obscure. So, in summary I think you're simply observing a valid argument form that doesn't have a flashy name like "Modus Tollens" or "Constructive Dilemma."