Spacetimes that are of zero Riemann curvature are all either subsets or quotients of Minkowski space. A few example of such manifolds would be Minkowski space minus some closed set $\mathbb{R}^{n-1, 1} \setminus U$, identifications of Minkowski space up to some translations such as cylinders and torus, identification of Minkowski space up to some boost (like Misner space), or more complex cases like the non-time orientable Minkowski space (Minkowski cylinder plus some identification up to some involution $(\theta, t) \to (\theta + \pi, -t)$) or some spacetime made by constructing a cone with the spatial section.
From those examples, we can see that there are indeed a lot of problems with simple connectedness and geodesic completeness for those examples. As mentionned by Maximal Ideal, that is indeed sufficient conditions for Minkowski space.
It is also enough that it be two-point homogeneous. Any flat spacetime is already maximally symmetric (in the sense that it has the full Poincaré group as Killing vector fields), but in addition the flow of those Killing vectors must be complete. Alternatively it is that for any points $p, q$, there is an isometry transporting $p$ to $q$ : $\phi(p) = q$, and any four points $p, q, r, s$ having the same geodesic distance, $d(p,q) = d(r,s)$, there is an isometry transporting $p$ and $q$ to $r$ and $s$
Alternatively, it can be homogeneous and isotropic : only single points need to be transported by isometries, and there is an isomorphism mapping any two unit vectors to each other : $\phi^* v = w$.
There is probably some other conditions that one could come up with, such as the causal structure having to obey the Minkowski space causal structure and the spatial slices having to obey Euclidian axioms (in particular the ones that are violated in those counter examples, such as the prolongation of lines or the number of incident points between two lines)