Let me complement PseudoNeo's excellent answer by actually writing down a motion of $E$ and showing that it intersects itself with multiplicity $-1$. Recall that $\mathbb{C}^2$ blown up at $(0,0)$ can be thought of as the space of ordered pairs $(z, \ell)$ where $z$ is a point of $\mathbb{C}^2$ and $\ell$ is a line through $z$ and through $(0,0)$. The exceptional fiber $E$ is the set of pairs of the form $((0,0),\ \ell)$ where $\ell$ can be any line through $(0,0)$.
In order to perturb this, I want to move to a set of the form $\{ \zeta(\ell), \ell \}$ where $\zeta$ is some continuous function which, to a line through the origin in $\mathbb{C}^2$, assigns a point on that line. We'll write $\ell$ in homogenous coordinates as $(x : y)$. So we need a continuous function $\zeta$ which, given $(x, y) \in \mathbb{C}^2 \setminus \{ (0,0) \}$, chooses some point on the line through $(x,y)$, so that $\zeta(x, y) = \zeta(\lambda x, \lambda y)$ for any nonzero $\lambda$.
Some experimentation produces
$$\zeta(x,y) := \left( \frac{x \overline{x}}{|x|^2+|y|^2},\ \frac{y \overline{x}}{|x|^2+|y|^2} \right).$$
Let $E_{moved}$ be the set of points $\left( \zeta(x,y), (x:y) \right)$. (If you want to reassure yourself that $E_{moved}$ is homotopic to $E$, consider the homotopy $\left( t\cdot \zeta(x,y), (x:y) \right)$, as $t$ goes from $1$ to $0$.)
Now $E$ intersects $E_{moved}$ when $\zeta(x,y)=(0,0)$, which happens when $(x:y) = (0:1)$. Near $\left( (0,0), (0:1) \right)$, local complex coordinates are $u$ and $v$, corresponding to the point $\left( (uv,u), (v:1) \right)$ in the blow up. In this chart, $E$ is given by $u=0$ and $E_{moved}$ is given by
$$u = \frac{\overline{v}}{1+|v|^2}.$$
The intersection takes place at $(u,v) = (0,0)$. Writing $u = u_1 + i u_2$ and $v = v_1 + i v_2$, the Jacobian of $v \mapsto \overline{v}/(1+|v|^2)$ is $\left( \begin{smallmatrix} 1 & 0 \\ 0 & -1 \end{smallmatrix} \right)$. The fact that this has determinant $-1$ indicates that the intersection with $u=0$ counts with sign $-1$.