I know how to do this for linear algebraic groups over an algebraically closed field $k$. I assume it works the same for Lie groups? I don't know Lie groups. Anyway, I hope this is helpful to you.
Let $G = \textrm{GL}_n$, let $R = k[T_{ij} : 1 \leq i, j \leq n]$, and let $A$ be the localization of $R$ at the function $\textrm{Det}$. Then $A = k[G]$ is the coordinate ring of $G$.
By definition, the tangent space of $G$ at $1_G$ is the $k$-vector space of derivations $\textrm{Der}_k(A,k)$ of $A$ into $k$, i.e. those $k$-linear maps $\delta: A \rightarrow k$ for which $\delta(fg) = f(1_G)\delta(g) + g(1_G) \delta(f)$ for all $f, g \in A$.
Every $\delta \in \textrm{Der}_k(R,k)$ extends uniquely, using the quotient rule, to an element of $\textrm{Der}_k(A,k)$. And $\textrm{Der}_k(R,k)$ is isomorphic as $k$-vector spaces to $M_n(k)$, the space of $n$ by $n$ matrices: every $\delta \in \textrm{Der}_k(R,k)$ is completely determined by its values on the coordinate functions $T_{ij}$, so associate $\delta$ to the matrix $(\delta(T_{ij})) \in M_n(k)$.
Now, let $L(G)$ be the subspace of $\textrm{Der}_k(A,A)$ (derivations from $A$ to itself) consisting of those $D$ which are left invariant: this means that $\lambda_x \circ D = D \circ \lambda_x$ for all $x \in G$. Here if $x \in G$, $\lambda_x$ is the $k$-algebra isomorphism $A \rightarrow A$ given by $\lambda_x(f)(y) = f(x^{-1}y)$ for all $y \in G$.
One can show that $\textrm{Der}_k(A,k)$ is isomorphic as $k$-vector spaces of $L(G)$: if $D \in L(G)$, we associate the element $\delta \in \textrm{Der}_k(A,k)$ given by $\delta(f) = D(f)(1_G)$. The inverse map is more complicated to describe: if $\delta \in \textrm{Der}_k(A,k)$, then we associate the element $D \in L(G)$ which sends an $f \in A$ to the element of $A$ given by the formula $x \mapsto \delta(\lambda_{x^{-1}}(f))$.
Now, $L(G)$ is naturally a Lie algebra with the bracket operation $[D,D'] = D \circ D' - D' \circ D$. Using the $k$-vector space isomorphism $L(G) \rightarrow \textrm{Der}_k(A,k)$, we transfer the bracket operation to $\textrm{Der}_k(A,k)$ to give $\textrm{Der}_k(A,k)$ the structure of a Lie algebra. The vector space $\textrm{Der}_k(A,k)$, considered as a Lie algebra, is called the Lie algebra of $G$ and is often denoted $\mathfrak g$.
Now you identify the Lie algebra of $G$ with $M_n(k)$, and you want to describe the bracket operation on $M_n(k)$ explicitly. So you need to transfer the bracket operation on $L(G)$ using the isomorphisms
$$M_n(k) \rightarrow \textrm{Der}_k(R,k) \rightarrow \textrm{Der}_k(A,k) \rightarrow L(G)$$
If you go through these isomorphisms, you will see that an element $D \in L(G)$, identified as an element of $M_n(k)$, is the $n$ by $n$ matrix whose $ij$th entry is $D(T_{ij})(1_G)$. Conversely, if you begin with an $n$ by $n$ matrix $A = (a_{ij})$, the corresponding element $D$ in $L(G)$ is given by the formula
$$D(T_{ij}) = \sum\limits_l T_{il}a_{lj}$$
Now, let $A, B \in M_n(k)$, and let $D,D'$ be the corresponding elements of $L(G)$. To show that the Lie bracket transfers over the way you want, it is enough to show that $D \circ D'$ is the element of $L(G)$ which corresponds to the product $AB$.
Let $C$ be the matrix corresponding to $D \circ D'$. The $ij$th entry of $C$ is $(D \circ D')(T_{ij})(1_G)$.
Now $D'(T_{ij}) = \sum\limits_l T_{il}b_{lj}$, and $D(T_{il}) = \sum\limits_s T_{is}a_{sl}$. Hence
$$D \circ D'(T_{ij}) = \sum\limits_{l,s} T_{is}a_{sl}b_{lj}$$ and so $c_{ij}$ is the evaluation of this polynomial at the identity matrix $1_G$. Now $T_{is}(1_G) = \delta_{is}$, and so
$$c_{ij} = \sum\limits_l a_{il}b_{lj}$$ done.