There may be a more compact way of doing it but I'm doing it in explicit separate steps with a ton of comments so that you can easily understand it:
% Define target value.
targetValue = 2.3
% Define test values. This is just for demo, you'd use your actual values.
testValues = 5 * rand(1, 10)
% Find differences
diffValues = testValues - targetValue
% We only want values less than the target value
% so those diffValues will be negative.
% We want the max of those, so set the others to -inf
diffValues(diffValues > 0) = -inf;
% Now we can find the index of the greatest value that
% is still less than the reference value.
[~, indexOfMax] = max(diffValues)
% Get the value from the testValues array
maxValue = testValues(indexOfMax)
