Many older movies seem to have vivid reds and particularly realistic or noticeable skin tones (they certainly seem to stand out from typical skin tones on TV or the majority of movies). This applies even in DVD or online versions and is not, given the range of material I've noticed the effect in, an artifact of special post processing or deliberate colour manipulation.
All the movies I've noticed the effect in are from the film era, especially from when colour became common to the late 1960's. I used to think it was just Technicolor but I've seen things recently that don't claim to be Technicolor that also show the effect.
This site claims the effect was due to the final print being constructed late in the process for separate black and white film strips for each primary colour allowing the final dyes to be very vivid and clear:
The rich colors that the Technicolor process gave came in part from the fact that the color was not added to the process until the final stages. The color information was recorded and processed as separate black and white images which were relatively easy to control and preserve.
Is this a good explanation?