To add to Gerben's answer:
If every vector $v$ in $V$ has at least one expression of the form $v=u+w$ with $u\in U$ and $w\in W$ ($U$ and $W$ subspaces of $V$), then $V=U+W$.
If every vector $v$ in $V$ has at most one (but possibly none) expression of the form $v=u+w$ with $u\in U$ and $w\in W$, then $U\cap W = \{0\}$.
So if every vector $v$ in $V$ has exactly one expression of the form $v=u+w$ with $u\in U$ and $w\in W$, then $V=U\oplus W$.
For more than two spaces you have to be a bit careful: it is no longer enough for the $U_i$ to be pairwise disjoint (that is, for $U_i\cap U_j$ to equal $\{0\}$ for $i\neq j$). For an example, take $V=\mathbb{R}^2$, $U_1$ the $x$-axis, $U_2$ the $y$-axis, and $U_3$ the line $x=y$. Then $U_1\cap U_2 = U_1\cap U_3 = U_2\cap U_3 = \{0\}$, but $V$ is not the direct sum of $U_1$ and $U_2$. Instead, you have that given subspaces $U_1,\ldots,U_m$ of $V$,
Each vector $v\in V$ has at least one expression of the form $v=u_1+\cdots + u_m$ with $u_i\in U_i$ if and only if $V=U_1+\cdots+U_m$ (the span of $U_1,\ldots,U_m$).
Each vector $v\in V$ has at most one (but possibly no) expression of the form $v=u_1+\cdots + u_m$ with $u_i\in U_i$ if and only if for each $i\in\{1,\ldots,m\}$, $U_i\cap(\mathop{\sum}_{i\neq j}U_j) = \{0\}$.