When the system is cold top up to about 1.5 bar and see if that has an affect. I wouldn't go as high as 2 bar as this is likely to cause the prv to discharge when the system is hot, the vessel condition and charge will have an affect on system pressure as well.
Why would air settle in the towel rails and not on the floor above? Air is less dense than water so you are correct to assume that it would settle at highest point of the system and usually does, however by design towel rails are taller and it's possible the air is getting stuck at the top and the water is circulating below it, happy to be proved wrong there though?