The solution $P(t)=P(0)e^{Lt}$ is valid for finite state space
(see for example, here). As explained for example here, $e^{Lt}$ is stochastic for each $t$. If $L$ is irreducible, then $e^{L}$ is primitive (actually positive, but I'm blanking out how to show this; in any case, the discrete-time Markov chain corresponding to $e^L$ is irreducible, and can not have any periodicity other than 1, so is aperiodic, hence primitive, which is enough). Then by Perron-Frobenius there is a spectral gap - i.e. the maximal eigenvalue is 1, corresponding generalized eigenspace is simple and contains unique eigenvector $\mu$ with positive entries that sum to 1, and all other eigenvalues have norm strictly $<1$. Since there are finitely many of them they all have norm at most some fixed $\lambda<1$. Then it follows that $L$ has the same generalized eigenspaces, one of eigenvalue $0$ (spanned by $\mu$) and all others with real part of eigenvalues $<\ln \lambda<0$. The $e^{tL}$ again has same generalized eigenspaces, one of eigenvalue $1$ spanned by $\mu$ and all other with eigenvalues of norm $<\lambda^t$. Writing a vector $\rho$ with entries summing to 1 using this generalized eigenspace decomposition we have
$$\rho=\mu+\sum c_i \rho_i$$
and then
$$e^{Lt}\rho=\mu+\sum c_i e^{Lt}\rho_i$$
But on each generalized eigenspace $e^{Lt}$ is the product of the scalar $\lambda_i^t$ and a matrix polynomial in $t$ (as in here), so each entry of $e^{Lt}\rho_i$ is of the form $\lambda_i^t P(t)$ for some fixed polynomial $P$, and in particular they are all bounded by $C\lambda^t$ for some $C$ (since $(\lambda_i/\lambda)^t<|C/P(t)|$). Since this is true for all pieces $\rho_i$, we get that each entry of $|e^{Lt}\rho-\mu|$ is bounded by $C\lambda^t$. Taking $D=-\ln \lambda$ this bound becomes $Ce^{-Dt}$ (with $C$ but not $D$ dependent on $\rho$).
In this finite-dimensional setting, it follows from this that $|e^{Lt}\rho-\mu|_{TV}<\hat{C}e^{-Dt}$ for some $\hat{C}$.
Why is the coefficient of $\mu$ equal to $1$?
Lemma: If $x$ is left generalized eigenvector of $A$ with generalized eigenvalue $a$ and $y$ right eigenvector of $A$ with eigenvalue $b$ and $a\neq b$ then $x \cdot y=0$.
Proof: $0=y^T \vec{0}= y^T(A-aId)^nx= (b-a)^n(y^Tx)$, so $y^Tx=0$.
Now because all other left generalized eigenspaces of $P(t)$ are orthogonal to the right eigenvector $\mathbb{1}=(1,...,1)$, so the sum of entries of $\rho$, aka $\rho\cdot\mathbb{1}$, is the coefficient of the $\mu$:
$$1=\rho\cdot\mathbb{1}=(c\mu +\sum c_i \rho_i)\cdot \mathbb{1}=c (\mu\cdot \mathbb{1})+0=c$$