Definition 1: Let $k$ be a field. It is called perfect field, if $\text{char} \ k=0$ or $\text{char} \ k=p$ with $k^p=k$.
Definition 2: $k$ has no properly bigger purely inseparable extension.
These definitions are equivalent.
Proof: $1 \Rightarrow 2$
If $\text{char} \ k=0$ I don't know what to do.
If $\text{char} \ k=p$. Suppose that exists an extension $E$ of $k$ which is properly bigger and is purely inseperable. Take $\alpha\in E$ such that $\alpha\notin k$. Then $\alpha^{p^n}\in k$ for some $n\geq 1$. Since $k=k^p$ then $\alpha^{p^n}=\beta_1^p$ for $\beta_1\in k$. Hence by freshman's dream $(\alpha^{p^{n-1}}-\beta_1)^p=0$ and $\alpha^{p^{n-1}}=\beta_1$ and if we continue in this way we get $\alpha^p=\beta_{n-1}\in k$ and $\beta_{n-1}=\beta_n^p$ for $\beta_n\in k$. Hence $\alpha^p=\beta_n^p$ and $(\alpha-\beta_n)^p=0$ so $\alpha=\beta_n\in k$ which is contradiction because $\alpha \notin k$.
$2 \Rightarrow 1$ Unfortunately I don't know how to prove this direction. I have tried by contradiction but it was useless.
Can anyone show how to prove it, please?
EDIT: An algebraic extension $E$ over $k$ is called purely inseparable if any of the following is true:
1) $[E:k]_s=1$.
2) All elements of $E$ are purely inseparable over $k$.
3) For any $\alpha\in E$, $\text{Irr}(\alpha,k,X)=X^{p^d}-a$ with $a\in k$, $d\geq 0$.
4) $E$ is generated over $k$ by a (possibly infinite) family $\{\alpha_i\}$ of elements all purely inseparable over $k$.
[Original answer below, answer to edited question first]
As definition $2$ does not apply to fields $k$ with $\operatorname{char}k=0$, the two definitions cannot be equivalent. If definition $1$ is considered only for fields of positive characteristic, then the two are equivalent. That is to say; for a field $k$ of positive characteristic $p$, the following two definitions are equivalent:
Definition 1: The field $k$ is called perfect if $k^p=k$.
Definition 2: The field $k$ is called perfect if it has no proper purely inseparable extension.
Your proof of the implication $1\ \Rightarrow\ 2$ is fine, though you might want to emphasize at the very start that you are assuming $k^p=k$. For a cleaner argument, you could work with the minimal $n\geq1$ such that $\alpha^{p^n}\in k$ to arrive at your conclusion more quickly.
For the converse, if $k$ has no purely inseparable extension then $X^{p^d}-a$ is reducible for all $a\in k$ and all $d\geq0$. In particular $X^p-a$ is reducible for every $a\in k$, where $X^p-a=(X-\alpha)^p$ for some $\alpha$ in a splitting field of $X^p-a$. This means $(X-\alpha)^m\in k[x]$ for some $0<m<p$. The coefficient of $X^{m-1}$ is $-m\alpha$ where $-m$ is a unit in $k$, and so we see that $\alpha\in k$. This proves that $k=k^p$.
Here is an outline of the proof of the contrapositive, where $k$ is a field:
If $k$ has a proper purely inseparable extension, then there exists an irreducible inseparable polynomial $f\in k[X]$. Then $f'=0$ so $\operatorname{char}k=p$ for some prime number $p$, and $f(X)=g(X^p)$ for some $g\in k[X]$. If $k^p=k$ then all coefficients of $g$ are $p$-th powers, so $f(X)=g(X^p)$ is a $p$-th power, contradicting the irreducibility of $f$. Hence $k^p\neq k$.
For the converse; if $\operatorname{char}k=p$ and $k^p\neq k$ then for every $a\in k-k^p$ the polynomial $f=x^p-a\in k[x]$ is irreducible and inseparable.
Note that a field $k$ has an inseparable extension if and only if there exists an irreducible inseparable polynomial $f\in k[x]$. This brings your definition $2$ in accordance with definition $1$ of these notes.