Yes, you have the right idea.
Let $\mathbb K$ be either $\mathbb R$ or $\mathbb C$ as appropriate. Suppose that the Banach space $X$ has a Schauder basis $\{x_n\}_{n=1}^\infty$, i.e., for every $x \in X$, there exists a unique sequence of scalars $\alpha_n \in \mathbb K$ such that
$$
x = \sum_{n=1}^\infty \alpha_n x_n,
$$
where this sum converges in the norm topology. We can renormalize so that $\Vert x_n \Vert =1$ for all $n$.
We fix such an $x \in X$ and show how to approximate it by elements from a countable set. Given $\varepsilon >0$, there exists $N \in \mathbb N$ such that
$$
\Vert x - \sum_{n=1}^N \alpha_n x_n \Vert < \varepsilon / 2.
$$
For each $\alpha_n \in \mathbb K$, we can find $\beta_n $ (in $\mathbb Q$ or $\mathbb Q + \mathbb Q i$ as appropriate) such that $| \alpha_n - \beta_n | < \varepsilon/ 2^{n+1}$.
Then, by the triangle inequality,
$$
\Vert x - \sum_{n=1}^N \beta_n x_n \Vert <
\Vert x - \sum_{n=1}^N \alpha_n x_n \Vert + \Vert \sum_{n=1}^N \alpha_n x_n - \sum_{n=1}^N \beta_n x_n \Vert
< \varepsilon/2 + \sum_{n=1}^N \varepsilon/2^{n+1} < \varepsilon.
$$
Thus every element in $X$ can be approximated by finite linear combinations of the elements of the Schauder basis, where the scalars come from $\mathbb Q$ or $\mathbb Q + \mathbb Q i$, as appropriate.
As for your second question: no, not every separable Banach space has a Schauder basis. This was a longstanding problem in the field, which was solved by Per Enflo in 1972 (for which he was awarded a
live goose!).
This result can be found in:
Enflo, Per (July 1973). "A counterexample to the approximation problem in Banach spaces". Acta Mathematica 130 (1): 309–317. doi:10.1007/BF02392270