Matt - You are pretty close to having the correct solution. The use of the cell array is a good idea for storing the data (as each column may have a different number of rows). It is just how to build the path to the file and its name that is (a little) tricky. Try the following
% there are 10 folders (or more, with assumption that directories and file are as
% you have described
n = 10;
% allocate slots in the cell array
data = cell(n,1);
% iterate
for k=1:n
% build the filename
filename = sprintf('D:\\%d\\%d.xlsx',k,k);
% read the first 100 rows of the first column
data{k}=xlsread(filename,'A1:A100');
end
The only catch with the above is that your Excel files may have more than 100 rows. To get around this you could do the following within the above loop
% read the all raw (numeric and text) data from the file
[~,~,rawData] = xlsread(filename);
% save the first column of data
data{k} = rawData(:,1);
Type doc xlsread for details on this function. We use the tilde to ignore the first two outputs of numeric and text data) and get all raw data from the first worksheet of the file. Then we extract the first column and save it to the cell array.
Try the above and see what happens!