Instead of regarding your algebra as a subalgebra of $C_b(\mathbb{R})$, I'll further enlarge the ambient algebra to $L^\infty(\mathbb{R})$. We note that any character on $C_\infty(\mathbb{R})$ can be extended to the algebra $\mathcal{A}$ you're concerned with, which can then be further extended to $L^\infty(\mathbb{R})$. Hence, the spectrum of $\mathcal{A}$ is an intermediate space between the spectrum of $L^\infty(\mathbb{R})$ (which we shall denote by $\Omega$) and the one-point compactification of $\mathbb{R}$.
Note that any element of $L^\infty(\mathbb{R})$ must restrict to a character on $C_\infty(\mathbb{R}) + \mathbb{C}$, whence it must restrict to the evaluation functional at some point in $\mathbb{R} \cup \infty$. For any $\varphi$ which restricts to $r \in \mathbb{R}$, one can show that it must satisfy $\varphi(f) = f(r)$ for all $f \in C_b(\mathbb{R})$. (I assume there is an easier way to prove this, presumably using the fact that $C_b(\mathbb{R})$ is the multiplier algebra of $C_\infty(\mathbb{R})$. But I'm not familiar with those, so the only way I know involves showing characters on $L^\infty(\mathbb{R})$ can be identified with ultrafilters on the Boolean algebra of measurable sets modulo a.e. equivalence. For details, see sections II and III of https://arxiv.org/abs/2306.02086 .) Hence, those characters don't "split" in the spectrum of $\mathcal{A}$. More precisely, if a character on $\mathcal{A}$ restricts to evaluation at $r \in \mathbb{R}$ on $C_\infty(\mathbb{R})$, then it must be evaluation at $r \in \mathbb{R}$ on the entirety of $\mathcal{A}$. So the spectrum of $\mathcal{A}$ is a compactification of $\mathbb{R}$.
We still need to figure out how the point at infinity splits. We note that $C_\infty(\mathbb{R})$ is an ideal in $\mathcal{A}$ and these characters correspond exactly to all characters that restrict to 0 on the said ideal, i.e., they correspond exactly to characters of $\mathcal{A}/C_\infty(\mathbb{R})$. The algebra generated by $e^{it}$ contains all continuous functions with period $2\pi$. Except the zero function, none of these functions is contained in $C_\infty(\mathbb{R})$, whence we see that $\mathcal{A}/C_\infty(\mathbb{R})$ is naturally isomorphic to the algebra generated by $e^{it}$, which is $C(\mathbb{T})$. One can then identify the spectrum of $\mathcal{A}/C_\infty(\mathbb{R})$ with $\mathbb{T}$, so the spectrum of $\mathcal{A}$ contains a copy of $\mathbb{T}$ at infinity.
To summarize, the spectrum of $\mathcal{A}$ can be divided into a copy of $\mathbb{R}$ and a copy of $\mathbb{T}$, both subspaces having their usual topologies. Since $\mathcal{A}$ is separable, the spectrum is second-countable, so to describe the topology I only need to describe convergence of sequences. $\mathbb{T}$ is closed in the spectrum, so a sequence solely in $\mathbb{T}$ will converge or diverge as in $\mathbb{T}$. The same goes for any bounded sequence in $\mathbb{R}$. For an unbounded sequence in $\mathbb{R}$, based on things we have obtained it's relatively easy to show that it only converges iff two conditions are met: 1. the sequence diverges to infinity; 2. modulo $2\pi$, the sequence converges in $\mathbb{T}$. In which case the sequence converges to the said limit in $\mathbb{T}$. Finally, for a sequence with both elements in $\mathbb{R}$ and $\mathbb{T}$: If the sequence only has finitely many elements in $\mathbb{R}$ or $\mathbb{T}$, then it reduces to one of the preceding cases. Otherwise, you can similarly show that it only converges iff two conditions are met: 1. the subsequence of all elements in $\mathbb{R}$ diverges to infinity; 2. reducing all elements in $\mathbb{R}$ modulo $2\pi$ to obtain a sequence purely in $\mathbb{T}$, then this sequence converges in $\mathbb{T}$. In which case the sequence converges, again, to the said limit in $\mathbb{T}$.
(I haven't come up with a more concise way to describe this space. If anyone has an idea as to how to do it, feel free to post in comments or edit my answer.)