I think this may be partly because one can use non-counter-style entries when using the optional argument to \item[<stuff>]. So, in that regard, you can set this manually so that the reference appears as you want:

\documentclass{article}
\usepackage{enumitem}
\usepackage[noabbrev]{cleveref}
\makeatletter
\newcommand{\setcreflabel}[1]{%
\protected@edef\cref@currentlabel{%
[\@tempa][#1][\cref@result]%
#1}}%
\makeatother
\begin{document}
\begin{enumerate}
\item \label{prob1}
\item[6.3] \setcreflabel{6.3}\label{prob63}
\item
From \cref{prob63}, some statement; From \cref{prob1}, some statement.
\end{enumerate}
\end{document}
The motivation here is to update \cref@currentlabel in an analogous way to how \refstepcounter updates \@currentlabel. In that way, when you issue \label, the correct reference content is written to the .aux:
\relax
\newlabel{prob1}{{1}{1}}
\newlabel{prob1@cref}{{[enumi][1][]1}{1}}
\newlabel{prob63}{{1}{1}}
\newlabel{prob63@cref}{{[enumi][6.3][]6.3}{1}}
From ?? 6.3and the error message is still undefined label. – dustin Sep 27 '14 at 14:38\setcreflabel{<something>}? – Werner Sep 27 '14 at 15:14\label{}as in the example. – dustin Sep 27 '14 at 15:15\usepackage[pdfencoding = auto, psdextra, bookmarksdepth = 4]{hyperref}loaded would this be affecting it? – dustin Sep 27 '14 at 15:32hyperrefdeals with cross-referencing in LaTeX. When dealing with cross-referencing problems, always consider including that you're usinghyperref. Always. I'll look into this further later. – Werner Sep 27 '14 at 19:09hyperreffirst thencleveref(see Which packages should be loaded afterhyperrefinstead of before?). Also issue\phantomsectionat the start of\setcreflabel. – Werner Sep 28 '14 at 03:32\phantomsectiondidnt work. – dustin Sep 28 '14 at 15:04hyperrefsetup before loadingcleverrefand I'm not getting??. Please provide a minimal example that replicates your problem. – Werner Sep 28 '14 at 15:45