Consider a statement like, "If London is in France, then London is in Asia."
AIUI, in classical/proportional logic, this is "true" because the antecedent is false. This (tenously) makes sense to me, along with the fact that $ P \rightarrow Q \Leftrightarrow ¬P \vee Q $. I'm not asking why vacuous truths are considered true, since there's endless discussion of that already.
However, the statement I opened with is clearly unsound, even if it is true. It would be incorrect, even in the context of a hypothetical/"possible world"/etc, to infer London actually being in Asia from it being in France. You cannot apply modus tollens and actually get $\{ P, (P \rightarrow Q) \} \rightarrow Q$ despite the conditional being true.
My problem with this is that my understanding of the "formal" part of formal theory is that we can do logical manipulations regardless of the specific content of the statement, as long as they have the correct forms. $\{P, (P \rightarrow Q)\} \rightarrow Q$ should always work, regardless of the specific content of the statements $P$ and $Q$. However, clearly, this doesn't work in this case.
I (think I) understand the distinction between syntatic inferences and semantic consequence, so I understand that just because $P \rightarrow Q$ doesn't mean that $P \Rightarrow Q$, but in that (this) case, why do we treat syntatic manipulations as "inferring" anything at all? Or is my understanding of formalism somehow incorrect?
IOW, what is the meaning of $\rightarrow$ as an "implication" - even in a syntatic, formalist, single-model sense - if we cannot always apply modus tollens to the result?

I disagree with your conclusion that the rule $\{P,P\rightarrow Q)\}\vdash Q$ does not apply here. (By the way, this rule is called "modus ponens". "Modus tollens" is the rule $\{P\rightarrow Q,\lnot Q\}\vdash \lnot P$.)
The statement "If London is in France, then London is in Asia" is true under a particular meaning of the non-logical words involved ("London", "France", "Asia", maybe even "is in"...). It is certainly not true under every interpretation of these words. So, as you correctly observe, letting $P = \text{London is in France}$ and $Q = \text{London is in Asia}$, the implication $P\rightarrow Q$ is not valid (i.e. true under every interpretation of the non-logical words involved).
But no matter what interpretations these words have, the entailment $\{P,P\rightarrow Q\}\vdash Q$ is sound.
This entailment says that if $P$ is true and $P\rightarrow Q$ is true, then $Q$ is true. Ok: Imagine $$P = \text{London is in France}$$ is true. And let's also imagine $$(P\rightarrow Q) = \text{If London is in France, then London is in Asia}$$ is true. Well, we're forced to conclude that London is also in Asia, i.e. $Q$ is true.
You write "It would be incorrect, even in the context of a hypothetical/"possible world"/etc, to infer London actually being in Asia from it being in France." Can you explain why you feel this way? Can't you imagine a world in which $P$, $P\rightarrow Q$, and $Q$ are all true (e.g. a world in which London is a city in France, which is a country in Asia)?