I'm exploring the claim that group theory is about symmetry.
Given a group $G$ that isn’t a set of structure preserving maps with composition, can you always interpret it as some kind of symmetry?
My answer to this is yes, because of Cayley's theorem. The procedure as I understand it is to look at G as purely a set, and consider all the structure preserving maps on it. Some subset of this set of transformations equipped with composition will have the same behaviour as the original group (it will be isomorphic). Hence every group can be represented as a subset of group of symmetries.
My question is what happens specifically when you try to turn $(\mathbb{R}, +)$ into a subset of some group of symmetries?
Turning my comments into an answer:
I suspect you're overthinking this, and not looking closely enough at the details of Cayley's theorem.
The right way to state Cayley's theorem is the following:
This is completely explicit about how $\mathcal{G}$ is isomorphic to a group of permutations of some set. And we can then use this to directly compute examples: if we look at $(\mathbb{R};+)$, we have that $G=\mathbb{R}$, $*=+$, and $\mathit{Cayley}(g)$ is the map $h\mapsto g+h$.
This is obscured by snappier-but-less-informative versions of Cayley's theorem like "Every group is isomorphic to a group of permutations." And the "explicit" form of Cayley's theorem above is no harder to prove than this less-useful form (in fact I don't know of a proof of the latter which doesn't in fact show the former).