Does this help? I've used leftmargin=! since leftmargin=* calculates things using the label width of the widest item, so labelwidth has no effect, for example.

\documentclass{article}
\usepackage{microtype}
\usepackage[T1]{fontenc}
\usepackage{enumitem}
\newcommand{\currentsection}{3.5}
\setlist[enumerate,1]{label=\currentsection.\arabic*.}
\begin{document}
\begin{enumerate}
\item ohai
\begin{enumerate}[align=left,widest=a,leftmargin=!]
\item the leftmost point of the left margin is aligned with the rightmost point of the left margin of the enclosing list
\end{enumerate}
\item ohai
\begin{enumerate}[align=left,widest=a,labelindent=5mm,leftmargin=!]
\item the leftmost point of the left margin is aligned with the rightmost point of the left margin of the enclosing list
\item the label begins 5mm to the right of the left margin
\end{enumerate}
\item ohai
\begin{enumerate}[align=left,widest=a,labelindent=5mm,labelwidth=15mm,leftmargin=!]
\item the leftmost point of the left margin is aligned with the rightmost point of the left margin of the enclosing list
\item the label begins 5mm to the right of the left margin
\item 15mm is allowed for the label
\end{enumerate}
\item ohai
\begin{enumerate}[align=left,widest=a,labelwidth=15mm,leftmargin=!]
\item the leftmost point of the left margin is aligned with the rightmost point of the left margin of the enclosing list
\item 15mm is allowed for the label
\end{enumerate}
\item ohai
\begin{enumerate}[align=left,widest=a,labelsep=5mm,leftmargin=!]
\item the leftmost point of the left margin is aligned with the rightmost point of the left margin of the enclosing list
\item 5mm is left between the rightmost side of the label and the start of the item body
\end{enumerate}
\item ohai
\begin{enumerate}[align=left,widest=a,itemindent=35mm,leftmargin=!]
\item the indentation of the item body, relative to the left margin is 135mm, so the left margin is now further left than in the other cases
\end{enumerate}
\end{enumerate}
\end{document}
If you set
\setlist[enumerate,2]{align=left,labelsep=0pt,leftmargin=*}
Then the label is aligned left within the width of the label. So there will be some space to the right of the label. If you use
[align=right,labelsep=0pt,leftmargin=!]
then you see the space disappear:

texdoc enumitem? Page 5. If you've read that, it would help to know what you don't understand. What output would you expect? Also, please give us a complete, minimal document we can copy-paste-compile to see what you see. – cfr Dec 13 '15 at 03:58leftmarginis then measured right from that point.itemindentis then measured rightwards again, from the rightmost point ofleftmargin.leftmargincontainslabelindentandlabelwidthand part oflabelsep.itemindentincludes the rest oflabelsep. – cfr Dec 13 '15 at 04:11align=rightand you'll see the label shifted to the right of the label width, so the gap disappears. (Pic below.) – cfr Dec 13 '15 at 04:32