First you need to set 8 columns, and then move to it. :) String columns should also be separated by the alignment operator &.
\begin{tabular}{l|l|l|l|l|l|l|l}
\multicolumn{4}{c}{Poblaci\'{o}n total en millones} &
\multicolumn{4}{c}{Porcentaje de poblaci\'{o}n rural}\\
\hline
1975 & 2001 & 2003 & 2015 & 1975 & 2001 & 2003 & 2015\\
\hline
10,3 & 15,4 & 16 & 17,9 & 21,6 & 14 & 13 & 9,8
\end{tabular}
To get a row between columns, just change the qualifier:
\begin{tabular}{l|l|l|l|l|l|l|l}
\multicolumn{4}{c|}{Poblaci\'{o}n total en millones} &
\multicolumn{4}{|c}{Porcentaje de poblaci\'{o}n rural}\\
\hline
1975 & 2001 & 2003 & 2015 & 1975 & 2001 & 2003 & 2015\\
\hline
10,3 & 15,4 & 16 & 17,9 & 21,6 & 14 & 13 & 9,8
\end{tabular}
More information on formatting the table is completed on WikiBooks. :)
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