iTunes WiFi sync has always been hit and miss for me over several generations of iPhones and iPads. I thought I'd give it another try with my new iPhone 6+ (iTunes 11.4.0.18 running on Win7 x64) but - as I've sadly come to expect - it seems to be broken out of the box. Great experience...
iTunes WiFi sync is such a useful feature in theory but it never worked properly for me, to the point where I had identified that its unreliable behaviour was causing corruption in my library and devices so switched it off and went back to 20th century wires... Though it's true that it seems to have regressed even further in iOS8 (ie: no connectivity at all).
I'm lucky enough that AirPlay appears to work ok - after some initial iOS8 instabilities. This kind of suggests my network is OK for Bonjour etc. Could the fact that my router provides simultaneous 2.4 & 5Ghz WiFi networks (different names) be an issue? I have both the iPhone and the laptop on the same 5Ghz network though.
One wishes Apple would be true to its mantra of providing stuff that "just works" for the masses. Sadly they seem to be sliding M$' direction ever faster...