Cyclic vectors in irreducible representations of simple Lie algebras
Summary The answer to the first question is affirmative and to the second question is negative, but for rather mundane reasons. In the simple Lie algebra case, cyclicity of ${\rm ad}\, a$ for some $a$ implies that $\frak{g}$ has rank $1$, in which case every non-zero element $x\in\frak{g}$ is cyclic in every simple module. On the other hand, for any $\frak{g}$, every $x\in\frak{g}$ acts cyclically on any one-dimensional module (e.g. the trivial representation). Thus in the higher rank case, all elements (even $x=0$) are trivial-cyclic and none are ad-cyclic. Moreover, all modules $V$ which admit a semisimple cyclic $x\in\frak{g}$ are weight multiplicity-free (WMF), which have been classified, and the corresponding cyclic elements can be explicitly described.
Details Assume that the ground field is not of characteristic $2$. It is easy to see that a simple Lie algebra $\frak{g}$ contains an ad-cyclic element only if $\frak{g}$ has rank $\ell=1$, so that ${\frak g}$ is a form of ${\frak sl}_2$. Indeed, by the standard properties of endomorphisms, the condtion "$A$ is cyclic" implies that the dimension of $\ker{A}$ is at most one, whereas for $A={\rm ad}\, x$, this dimension is at least $\ell$ by the definition of rank; thus $\ell\leq 1$. Conversely, every non-zero element $x$ of a simple rank $1$ Lie algebra acts cyclically in every finite-dimensional simple module: extend the scalars to an algebraically closed field and consider separately the cases of semisimple and nilpotent $x$.
A semisimple endomorphism (or a diagonal matrix) is cyclic iff its eigenvalues are distinct. Let $h\in{\frak h}$ be a semisimple element of a split semisimple Lie algebra $\frak{g}$ with a Cartan subalgebra ${\frak h}$ and $V$ an $N$-dimensional $\frak{g}$-module with weights $\lambda_1,\ldots,\lambda_N\in {\frak h}^*$. Then the matrix of $h$ relative to a weight basis of $V$ is diagonal with eigenvalues $\lambda_i(h)$ and $h$ acts cyclically on $V$ iff $\lambda_i(h)$ are pairwise non-equal. In particular, this is possible only if $V$ is weight multiplicity-free (WMF), and all such modules have been classified (consistent with the above, the adjoint module is WMF iff ${\frak g}$ is a direct sum of several copies of ${\frak sl}_2$). For example, in characteristic $0$, if ${\frak g}={\frak sl}_n$, the simple WMF modules are exhausted by the symmetric powers $S^k W$ of the defining module $W$, their duals, and the exterior powers $\Lambda^k W$ of $W$, and the necessary condition for $h$ to act cyclically on $V$ is that $h$ is regular (equivalently, $h$ acts cyclically on $W$, i.e. has distinct eigenvalues). Of course, this condition is not sufficient in general. For example, if $V=S^2 W$ and $h$ is diagonal with eigenvalues $a_i$ that sum to $0$, $h$ is cyclic on $V$ iff all $a_i+a_j, 1\leq i\leq j\leq n$ are pairwise distinct. For $n\geq 3$, this is clearly stronger than just all $a_i$ being pairwise distinct.
Note, however, that reducible WMF modules also exist: for example, let $\frak{g}={\frak sl}_n$ and $V=W\oplus\Lambda^2 W$, then $V$ is WMF and every diagonal $h$ with $n$ distinct eigenvalues $a_i$ satisfying appropriate additional inequalities acts cyclically on $V$. Thus contrary to OP's Remark 1, an element of ${\frak g}$ can act cyclically on a reducible module.
If $e$ is a nilpotent element acting cyclically on a $\frak{g}$-module $V$ then $V$ has to be simple with respect to the corresponding ${\frak sl}_2$-subalgebra, so that the weights of $V$ belong to a single line. This places severe constraints on the possible data. For a simple classical Lie algebra ${\frak g}\ne{\frak sl}_2$ and a non-trivial module $V$, this leaves only the cases of ${\frak g}={\frak sl}_n$ and $V$ the defining module or its dual, and a symplectic or odd orthogonal ${\frak g}$ and the defining ("vector") module $V$, with the element $e$ being a principal nilpotent in all cases.
Finally, if $x=s+n$ is the Jordan decomposition of a general element acting cyclically on a $\frak{g}$-module $V$ then the centralizer $Z(s)$ of the semisimple part $s$ is a reductive subalebra containing $x$, so that $V$ is a $Z(s)$-module with a cyclic action of $x$. This provides an approach to classifying general cyclic pairs $(V,x)$.