To answer the first question: Only when $G$ is abelian. In fact, if $G$ is not abelian and has dimension $2d$, then there is no element of $H^2(G,\mathbb{R})$ whose $d$-th power is nonzero in $H^{2d}(G,\mathbb{R})$ (just look at the representation by bi-invariant forms), and there would have to be such an element if there were going to be even a symplectic structure on $G$, much less a Kähler structure. Conversely, if $G$ is abelian, then, yes, since $G=\mathbb{R}^{2d}/\mathbb{Z}^{2d}$, and, for any left-invariant complex structure, $G$ is $\mathbb{C}^d/\Lambda$, where $\Lambda\subset\mathbb{C}^d$ is a lattice (i.e., a discrete subgroup of maximal rank $2d$). Thus, there is a left-invariant Kähler structure, for example, (though there are others).
Added on 21 Jan 2017: As for your second question, I believe I have a partial answer, which is 'If the center of $G$ is finite (i.e., $G$ is semisimple), then $G$ does not possess a balanced metric'. Here is why: It is my understanding that, if $G$ is a compact Lie group and $J$ is a left-invariant complex structure, then $J$ is one of the complex structures constructed by Samelson and Wang. (See H.C. Wang, Closed Manifolds with Homogeneous Complex Structure, American Journal of Mathematics 76 (1954),1–32, which seems to indicate this though it doesn't state it explicitly. Also, see the article mentioned by François in the comments below.)
In such cases, there exists a maximal toral subgroup $T\subset G$ that is $J$-complex, and the quotient $G/T$ inherits a complex structure such that the quotient map $\pi:G\to G/T$ is holomorphic. Moreover, $G/T$ is not only Kähler, but an algebraic complex manifold to boot (in fact, it's the complete flag variety of $G$).
In particular, $G/T$ contains an algebraic (complex) hypersurface $Z\subset G/T$, whose preimage $X=\pi^{-1}(Z)\subset G$ is therefore a compact complex hypersurface in $G$. Now if $\omega$ were a positive $(1,1)$-form on $G$ (with respect to the complex structure $J$) such that $\omega^{d-1}$ were closed (where $2d$ is the dimension of $G$), then the integral of $\omega^{d-1}$ over $X$ would be positive. In particular, it would follow that the homology class of $X$ in $H_{2d-2}(G,\mathbb{R})$ were nonzero.
However, when $G$ is semi-simple (i.e., when its center is finite), we know by the Whitehead Lemma that $H_2(G,\mathbb{R}) = 0$, so Poincaré Duality implies that $H_{2d-2}(G,\mathbb{R})=0$ as well, contradicting the fact that the real homology class of $X$ must be nonzero.
I believe a more careful analysis of the cohomology ring of $G$ when the center of $G$ has positive dimension will lead to the result that $G$ can carry a balanced metric only when $G$ is abelian.