I don't quite understand your definition of the left-invariant vector field (notably you didn't explain what $\mu$ is and how it can be used as exponent both to $\phi$ and to $X$). However a basic description of the situation is not hard to grasp.
A one-parameter subgroup $\phi$ is a parametrised curve in $G$ that passes through the identity element $e\in G$ (at $t=0$). It has a tangent vector at $e$, which is an element of the tangent space at $e$. The requirements for a one-parameter subgroup make that $\phi$ is entirely determined by this tangent vector, and can be recovered by exponentiation; this means the set of one-parameter subgroups is naturally in bijection with the tangent space of $G$ at $e$.
Now describing a vector field means giving a tangent vector at every point of $G$, whereas $\phi$ only gives such vector on the points it passes through. But a Lie group, as opposed to a manifold, has an intrinsic symmetry: it acts on itself by left-multiplication, and this action is transitive (any chosen point $a$ can be sent to another chose point $b$ by an appropriate group element acting). In fact the action is simply transitive: there is exactly one group element that gets you from $a$ to $b$. In particular, for any point $g\in G$ there is exactly one group element whose action sends $e$ to $g$; not surprisingly, that group element in $g$ itself. Now if one gives a tangent vector $X_e$ at $e$, one can use the tangent map of the action (left-multiplication by $g$) to obtain a tangent vector $X_g$ at $g$. Doing so for all $g\in G$ gives a vector field $g\mapsto X_g$ on $G$. Using the fact that left-multiplication is an action, one easily checks that this field is left-invariant (i.e., the tangent map to the left-multiplication that sends $a$ to $b$ sends $X_a$ to $X_b$). Also all left-invariant vector fields are like this, since the way we obtained $X_g$ from $X_e$ was just an instance of the left-invariance requirement. In summary, the tangent space of $G$ at $e$ is naturally in bijection with the space of left-invariant vector fields on $G$. Composing with the earlier bijection, the latter is also in bijection with the set of one-parameter subgroups of$~G$.
(One checks easily that, for those points of $G$ through which the curve passes, the vector field associated to a one-parameter subgroups coincides with the tangent vectors of the curve.)
What differs in the case of a manifold is that there is no given simply transitive action to transport vectors by. This means the is no notion of (left-)invariance, and consequently it is not possible to go from a set of vectors defined only on the points of the curve to a vector field defined everywhere.