We did the Rhine route last year in the opposite direction to your plan from Mainz (where you turn off the Rhine onto the Main for Frankfurt, I presume) to the Ijmuiden ferry port. Navigation was pretty easy, it was well signposted. Some parts are very scenic, like the Rhine gorge, others less so but even the industrial parts were interesting. We used the Ciccerone guide book but we stayed on hotels so can't help with campsites.
As the Rhine doesn't flow through Amsterdam, I suggest to ride to Utrecht then follow the Amsterdam-Rhine canal to the Rhine. Highlights include Xanten, a lovely walled town near the Dutch border, Wonderworld Wunderland, nuclear power station turned into a theme park and the Rhine gorge south of Koblenz.