To me, the most intuitive way to understand this identification is to follow along Kurt G.'s comment and to just work with the smooth structure of $G$ as a manifold and multiplication as a smooth map.
A matrix Lie group $G\leq \operatorname{GL}(n)$ has the smooth structure of an embedded submanifold of the surrounding Euclidian space $\mathbb{R}^{n^2}$ with its natural smooth structure given by the identity chart.
All this means is that maps to and from $G$ are smooth (in the manifold sense) if and only if they are smooth in the Euclidian sense, i.e. when $G$ is seen as a subset of $\mathbb{R}^{n^2}$. Differentiability and the derivative of a map on the subset $G$ are defined by the existence of an extension to an open neighbourhood of $G$.
On the one hand, this allows us to identify tangent vectors as
$$T_g G = \left\{\frac{d}{dt}_{|t=0} \gamma : \quad \gamma\colon (-\varepsilon,\varepsilon)\to G, \gamma(0) = g\right\}\subseteq M_{n\times n},$$ where we just derive curves in $\mathbb{R}^{n^2}$ in the usual way.
On the other hand, we can see that matrix multiplication is a bilinear map $$m\colon M_{n\times n} \times M_{n\times n}\to M_{n\times n},\quad m(A,B) = AB.$$
As for any bilinear map, it is then straightforward to show
$$(dm)_{(A,B)}(V,W) =\frac{d}{dt}_{t=0}m(A+tV,B+tW) = m(A,W) + m(V,B) = AW + VB.$$
The multiplication on $G$ has an extension to all of $\mathbb{R}^{n^2}$ - it was defined as a restriction. This implies that the derivative of the restriction $m_{|G}$ to $G$ is given by the restriction $dm_{|TG\times TG}$ of the derivative on $\mathbb{R}^{n^2}\times \mathbb{R}^{n^2}$ to the tangent space.
We obtain the derivative of left-multiplication at $A$ by setting $V = 0$:
$$(dL_A)_B W = dm_{(A,B)}(0,W) = AW = L_AW.$$
Alternatively, you can consider multiplication $L_A\colon G\to G$ with a fixed matrix from the left directly, i.e. $L_A(X) = AX.$ This map is linear, and as for any linear map
$$(dL_A)_X W = L_AW = AW,$$ which can be seen directly by applying the definition of the total derivative in Euclidian space and using the linearity of $L_A$ once.
Again, since the smooth structure on $G$ is given by the smooth structure on the surrounding $\mathbb{R}^{n^2}$, this shows $$(L_A)_* = L_A\colon TG\to TG.$$
The "confusion" stems from the fact that the symbol $L_A$ does not contain all the information about the map. It just means "left-multiplication with $A$" and tells us nothing about the domain and codomain. If we evaluate the derivative of left-multiplication with $A$ at any point $X$ applied to a tangent vector $W$, which is also a matrix, we obtain the tangent vector $AW$ at $AX$. It can be expressed as $L_A$, but with different domain and codomain than the original map.