Every 2-transitive Lie group action on a connected smooth manifold (of dim ?) cannot be Riemannian because it cannot preserve a metric. The action can at most take two equidistant points to another pair of equidistant points.
Is a quotient of a Lie-homogeneous again Lie-homogeneous?
No. By Mostow’s result, higher genus compact orientable surfaces are not Lie-homogeneous, but their universal cover is which is Lie-homogeneous.
The fact that they are not Riemannian homogeneous is easily proven by Riemann surface techniques. 7
Classification of connected isotropic Riemannian manifolds
Classification of every connected isotropic Riemannian manifolds is actually very simple: they are precisely all globally symmetric spaces of rank 1. These are also precisely all the Riemannian manifolds whose isometry group act transitively on all pairs of equidistant points.