I wonder, what exactly does it mean for a Lie group to be semi-simple geometrically?
I know that any Lie group is a group and a smooth manifold simultaneously, so it can be considered merely as a vector field in dimension one. However, I don't get the geometrical philosophy behind the simplicity of a Lie group. What does the condition tell us about a vector field associated with the group itself?
How can one describe geometrically the condition of simplicity (or semi-simplicity) of a Lie group?
The sentence "so it can be considered merely as a vector field in dimension one" makes no sense as a manifold is not the same thing as a vector field. There is no single vector field canonically associated with a group. A Lie group is a smooth manifold $G$ equipped with a group operation which happens to be a smooth map $G\times G\to G$, don't read more into it.
For a connected Lie group, Cartan's second criterion says that $G$ is semi-simple if and only if its Killing form $B\colon \mathfrak{g}\times\mathfrak{g}\to\Bbb R$, given by $$B(X,Y) = {\rm tr}({\rm ad}(X){\rm ad}(Y)),$$is non-degenerate. If $G$ is assumed to be compact, then $-B$ is positive-definite and therefore defines a left-invariant Riemannian (Einstein) metric on $G$.