When one talks of a topological manifold being locally homeomorphic to $\mathbb{R}^{n}$ is it meant that the topology of the manifold is locally identical to a Euclidean topology such that we can represent points on the manifold (locally) in the same manner that we can for $\mathbb{R}^{n}$, i.e. as $n$-tuples of real numbers?
I must admit I find the whole concept of topology quite confusing, I've read things such as "a topology on a manifold endows it with a primitive notion of geometrical structure without the need to introduce the notion of a metric etc." What exactly is meant by this? In physics, particularly general relativity, space time is taken as a topological manifold, and I know that the manifold has a topology defined on it is key, but I don't really understand the conceptual significance of it?
When we say that a topological space $X$ is a topological manifold being locally homeomorphic to $\mathbb{R}^n$ if for each $x\in X$ there exists an open set $U$ containing $x$ with a continuous function $\phi_U:U\rightarrow \mathbb{R}^n$ such that $\phi_U$ induces an homeomorphism between $U$ and $\phi_U(U)$. This is the ground definition. The $(U,\phi_U)$ are called charts.
Now one usually requires additional "properties" (they are quite technical, in most cases they are obvious) namely the topology on $X$ should be Hausdorff and countable at infinity.
The idea behind your quote is (IMO) that generally you just don't want to work with "topological" manifold but you want to work on "differentiable" manifold or "holomorphic" manifold (to name but a few). Now those additional structures are quite hard to define out of nowhere.
If $X$ is a topological manifold with a set of charts $\{(U,\phi_U)\}$ we say that they define a "differentiable" manifold if for any chart $U,V$ such that $U\cap V\neq \emptyset$ we have that :
$$\phi_U\circ\phi_V^{-1}:\phi_V(U\cap V)\rightarrow \phi_U(U\cap V) $$
is a diffeomorphism. Remark that we already know that this is a homeomorphism but because $\phi_V(U\cap V)$ and $ \phi_U(U\cap V)$ are both included in $\mathbb{R}^n$ we can talk about diffeomorphism.
Hence we see that to define a geometric structure on some space $X$ we need to get a structure of topological manifold for $X$ and then require all the transition to respect the geometric structure in question.
That is why the topological manifold is the "primitive notion of geometric structure" it is a tool that allows us to put some significant geometric structure (differentiable, holomorphic...) on a space.