\First is not expandable and can therefore not be used in \numexpr.
The package arrayjobx provides the following alternative:
\check<arrayname> extracts the desired value and stores it in \cachedata that can now be used in \numexpr and other places:
\documentclass{letter}
\usepackage{arrayjobx}
\begin{document}
\newarray\First
\readarray{First}{10&8&3}
\newcounter{ExpOneTotal}
\First(1)
\checkFirst(1)\cachedata~=~\the\numexpr\cachedata\relax
\addtocounter{ExpOneTotal}{\cachedata}
My counter is: \theExpOneTotal~=~\First(1)
\end{document}

With calculations of row and column sums:
\documentclass{letter}
\usepackage{arrayjobx}
\usepackage{booktabs}
\begin{document}
\newarray\First
\newarray\Second
\newarray\Third
\readarray{First}{10&8&3}
\readarray{Second}{1&7&8}
\readarray{Third}{1&5&16}
\newcounter{ExpTotali}
\newcounter{ExpTotalii}
\newcounter{ExpTotaliii}
\def\AddTotal#1(#2){%
\csname check#1\endcsname({#2})%
\cachedata
\addtocounter{ExpTotal\romannumeral#2}\cachedata
}
\newcounter{ExpTotalSum}
\newcounter{ExpSum}
\makeatletter
\def\ExpSum#1(#2){%
\setcounter{ExpSum}{0}%
\begingroup
\@for\I:=#2\do{%
\csname check#1\endcsname(\I)%
\addtocounter{ExpSum}{\cachedata}%
}%
\endgroup
\theExpSum
\addtocounter{ExpTotalSum}{\value{ExpSum}}%
}
\makeatother
\begin{tabular}{ccccc}
\toprule
Experiment & a & b & c & TOTAL \\
\midrule
Exp 1 & \AddTotal{First}(1) & \AddTotal{First}(2) & \AddTotal{First}(3) &
\ExpSum{First}(1,2,3) \\
Exp 2 & \AddTotal{Second}(1) & \AddTotal{Second}(2) & \AddTotal{Second}(3) &
\ExpSum{Second}(1,2,3) \\
Exp 3 & \AddTotal{Third}(1) & \AddTotal{Third}(2) & \AddTotal{Third}(3) &
\ExpSum{Third}(1,2,3) \\
\midrule
TOTAL & \theExpTotali & \theExpTotalii & \theExpTotaliii &
\theExpTotalSum \\
\bottomrule
\end{tabular}
\end{document}

With alignment of the numbers via package siunitx:
\documentclass{letter}
\usepackage{arrayjobx}
\usepackage{booktabs}
\usepackage{siunitx}
\begin{document}
\newarray\First
\newarray\Second
\newarray\Third
\readarray{First}{10&8&3}
\readarray{Second}{1&7&8}
\readarray{Third}{1&5&16}
\newcounter{ExpTotali}
\newcounter{ExpTotalii}
\newcounter{ExpTotaliii}
\def\AddTotal#1(#2){%
\csname check#1\endcsname({#2})%
\addtocounter{ExpTotal\romannumeral#2}\cachedata
\global\let\CD\cachedata
}
\newcounter{ExpTotalSum}
\newcounter{ExpSum}
\makeatletter
\def\ExpSum#1(#2){%
\setcounter{ExpSum}{0}%
\begingroup
\@for\I:=#2\do{%
\csname check#1\endcsname(\I)%
\addtocounter{ExpSum}{\cachedata}%
}%
\endgroup
\addtocounter{ExpTotalSum}{\value{ExpSum}}%
}
\makeatother
\begin{tabular}{c*{4}{S[table-format=2]}}
\toprule
Experiment & a & b & c & TOTAL \\
\midrule
Exp 1
& {\AddTotal{First}(1)}\CD
& {\AddTotal{First}(2)}\CD
& {\AddTotal{First}(3)}\CD
& {\ExpSum{First}(1,2,3)}\theExpSum \\
Exp 2
& {\AddTotal{Second}(1)}\CD
& {\AddTotal{Second}(2)}\CD
& {\AddTotal{Second}(3)}\CD
& {\ExpSum{Second}(1,2,3)}\theExpSum \\
Exp 3
& {\AddTotal{Third}(1)}\CD
& {\AddTotal{Third}(2)}\CD
& {\AddTotal{Third}(3)}\CD
& {\ExpSum{Third}(1,2,3)}\theExpSum \\
\midrule
TOTAL & \theExpTotali & \theExpTotalii & \theExpTotaliii &
\theExpTotalSum \\
\bottomrule
\end{tabular}
\end{document}
