A space is first-countable if for each point $x$ there is a single sequence of neighborhoods such that every neighborhood of $x$ contains in some neighborhood in the sequence. Although for each specific neighborhood $V$ we can easily find a sequence with some element contained in $V$, we can't necessarily find a single sequence which works for every such neighborhood. (This is similar to the reason why the reals are uncountable, even though any specific real can be put on a list.)
This just shows why first-countability is not obviously trivial. It turns out that it is really nontrivial: there are lots of non-first-countable sequences. For example, consider the order topology on $\omega_1+1$. Every open neighborhood of $\omega_1$ here contains a neighborhood of the form $(\alpha, \omega_1]$ for $\alpha$ a countable ordinal. But the supremum of countably many countable ordinals is countable, so for any sequence $U_i$ ($i\in\mathbb{N}$) of neighborhoods of $\omega_1$ contains a neighborhood of the form $(\beta, \omega_1]$ for some countable ordinal $\beta$. But then the neighborhood $(\beta+1, \omega_1]$ doesn't contain any of the neighborhoods $U_i$.
EDIT: here's a much better example, not requiring ordinals at all: the cocountable topology on any uncountable set $S$. For any sequence of neighborhoods $(U_i)_{i\in\mathbb{N}}$ of a point $x$, the intersection $\bigcap U_i$ is again cocountable, and hence uncountable (since $S$ is uncountable). Pick $s\in \bigcap U_i$, $s\not=x$; then $(\bigcap U_i)\setminus\{s\}$ is a neighborhood of $x$ not containing any of the $U_i$s.
Interestingly, first countability is nontrivially nontrivial: showing that a space is not first countable generally requires using a principle of the form "the union of countably many "small" sets is "small,"" and such principles are generally not true without some amount of the axiom of choice. For instance, it is consistent with ZF that every infinite set is a countable union of sets of strictly smaller cardinality! In fact, I don't offhand know of an example of a space which is provably non-first-countable in ZF alone (and I've now asked a question about this).
(Incidentally, there are some neat examples if choice fails sufficiently badly - e.g. the cofinite topology on any amorphous set, if such a set exists.)