I will try to give a detailed proof of the second question by ItsNotObvious above. My justification for answering a year-old, already answered question, which is probably a very well-known fact as well, is that I couldn't find a detailed proof of it anywhere in the literature.
Proposition: Let $M$ be a connected smooth manifold. Then for every two points $p,q \in M$ there exists a smooth (i.e. smooth at all of $(0,1)$) path $$\gamma: [0,1] \rightarrow M$$ such that $\gamma(0)=p$ and $\gamma(1)=q$.
Proof. We will establish the proof by proving two lemmas, which when combined imply the proposition. First we need to facts.
Fact 1: Every n-dimensional (not necessarily smooth) manifold $M$ admits a covering by coordinate charts $(U_{i}, \varphi_{i})$, where each of the $U_{i}$ is homeomorphically mapped by $\varphi_{i}$ to an open ball around the origin in $\mathbb{R}^{n}$. In particular $M$ is locally path-connected.
In fact the above covering can be chosen to be countable, but we won't need that fact.
Fact 2: A locally path-connected topological space is connected, if and only if it is path-connected. Hence connected manifolds are path-connected.
More or less detailed proofs of those facts can be found in J.M. Lee “Introduction to Smooth Manifolds” Lemma 1.6. (Fact 1) and in “Introduction to Topological Manifolds” Proposition 4.26 e) (Fact 2) by the same author.
Lemma 1: Let $M$ be a connected smooth manifold. Then for every two points $p,q \in M$ there exists a path, which is non-smooth at only finitely many points in $(0,1)$, and such that for all $t \in [0,1]$ all left and right derivatives of any order exist (i.e. $\gamma$ is piecewise smooth).
Proof. Let $\gamma: [0,1] \rightarrow M$ be a path joining $p$ and $q$. By Fact 1 there is a cover $\{U_{i}\}_{i \in I}$ of $\gamma([0,1])$ consisting of charts $(U_{i},\varphi_{i})$, such that each of the open sets $U_{i}$ is homeomorphic to an open ball around the origin via $\varphi_{i}$. Now the preimages $\gamma^{-1}(U_{i})$ form an open cover of $[0,1]$. By the Lebesgue Lemma there is an $n \in \mathbb{N}$, such that the finitely many intervals $$[\frac{k}{n},\frac{k+1}{n}] \qquad k=0,…,n-1$$ cover $[0,1]$ and such that for every $k$ there exists a $j_{k} \in I$ with $\gamma([\frac{k}{n},\frac{k+1}{n}]) \subset U_{j_{k}}$.
Let $\alpha_{k}: [\frac{k}{n},\frac{k+1}{n}] \rightarrow \varphi_{j_{k}}(U_{j_{k}})$ be a straight line, parametrized by $[\frac{k}{n},\frac{k+1}{n}]$ connecting $\varphi_{j_{k}}(\gamma(\frac{k}{n}))$ with $\varphi_{j_{k}}(\gamma(\frac{k+1}{n}))$, which is possible as $\varphi_{j_{k}}(U_{j_{k}})$ is an open ball and thus convex. Now define a new path $$\tilde{\gamma}: [0,1] \rightarrow M$$ piecewise by $$\tilde{\gamma}(t) = \varphi_{j_{k}}^{-1}(\alpha_{k}(t)), \qquad \text{if} \quad t \in [\frac{k}{n},\frac{k+1}{n}]$$ It is clear from the definition that $\tilde{\gamma}$ is a piecewise smooth path joining $p$ and $q$.
Lemma 2: Let $\gamma_{1}, \gamma_{2}: [0,1] \rightarrow M$ be two smooth curves with $\gamma_{1}(1)=\gamma_{2}(0)$. There is a smooth curve $$\gamma: [0,1] \rightarrow M$$ such that $\gamma(0)=\gamma_{1}(0)$ and $\gamma(1)=\gamma_{2}(1)$. In particular any two points $p,q \in M$, which can be connected by a piecewise smooth curve can be connected by a smooth curve.
Proof. Define $$\sigma_{1}: [0,1] \rightarrow [0,1], \qquad t \mapsto 1-e^{-\frac{1}{1-t}+1}$$ $$\sigma_{2}: [0,1] \rightarrow [0,1], \qquad t \mapsto e^{-\frac{1}{t}+1}$$ Both maps are homeomorphisms of $[0,1]$ onto itself. Consider the path $$\gamma:=(\gamma_{1} \circ \sigma_{1}) \star (\gamma_{2} \circ \sigma_{2})$$ where $\star$ denotes the composition of two paths. It is clear that $\gamma$ is smooth everywhere on $(0,1)$, except for possibly $t=\frac{1}{2}$.
Denote by $\partial_{+}$ the right derivative and by $\partial_{-}$ the left derivative. By applying the chain rule for semi-differentiable functions it is easy to see that $$\partial_{+}\gamma(\frac{1}{2})=\partial_{+}(\gamma_{1} \circ \sigma_{1})(1)=\partial_{+}\gamma_{1}(\sigma_{1}(1)) \partial_{+}{\sigma_{1}(1)}= \partial_{+}\gamma_{1}(\sigma_{1}(1)) \cdot 0=0$$ and likewise $\partial_{-}\gamma(\frac{1}{2})=0$. This shows in particular that the left and the right derivative of $\gamma$ in $\frac{1}{2}$ agree, and a similar calculation shows that all higher left and right derivatives agree at $\frac{1}{2}$ as well. Hence $\gamma$ is smooth
Putting the two facts and the two lemmas together gives the proof of the proposition.
Edit:
One could alternatively prove Lemma 1 by showing that for a given point $p \in M$ the set of points which can be connected by a piecewise smooth path with $p$ is non-empty and both open and closed in $M$ and hence all of $M$, as $M$ is connected. The proof is almost the same as the proof of Fact 2. Roughly speaking, in the proof of Fact 2 (sketched by Qiaochu in his answer) you replace "path" by "piecewise smooth path" everywhere. I just realized this after posting my answer.