The belt's outer width is more or less the same width as the top of the groove; but more importantly, you are right that it does not contact the groove floor.
Measuring with rope won't give a very accurate answer because the lines of contact will be wrong, but as Redsetter says, there are dedicated calculators or the formula for the purpose.
V ee-Belts are designated by their circumferences and standard widths each designated by a code-letter, and the pulley groove reflects that, so you need know:
– the width of the top of the groove, to establish the belt type;
– the outside diameters of the pulleys (some, by no means all, are marked);
– the distance between centres.
Obviously too the machine needs a good range of adjustment from slack enough to slip the belt off completely or to change ratio on a stepped-pulley (move the smaller end first); to correct tension for running.
A tip: having bought and fitted the correct belt: cut the label from its box and keep it in a safe place so you know the designation (width-code and circumference) for future replacements, by which time the markings on the belt itself may have become illegible.
Similarly with the packaging-labels for other standard parts that wear more rapidly than the machine as whole.