The problem you have is that Bavaria and Neuschwanstein are in Germany (although Neuschwanstein is so close to the Austrian border the problem can be mitigated) but most of the Alps are in Austria or Switzerland. The reason this is a problem is because hiring a car in country A and dehiring in country B attracts high financial penalties; the car hire companies really dislike it.
Getting to Neuschwanstein is pretty easy by public transport as this page (http://www.neuschwanstein.de/englisch/tourist/howtoget.htm) on the Neuschwanstein castle homepage will show. Check the DB website (http://www.bahn.co.uk is the english language version) for deals for a family travelling.
Getting around the Alps is also perfectly doable via public transport although potentially expensive. http://www.myswitzerland.com has details of passes you can use that either include the major touristy attractions such as cable cars and certain trains, or else they offer % discounts for those attractions.
It really depends on your exact proposed itinerary, when, how long for and what your budget is. Conceivably you could buy rail passes (as a random example) for the entire trip from England through to Italy. http://www.seat61.com will give you info re trains throughout Europe (1st class is unnecessary, stick with 2nd) whilst the aforementioned DB site will give you a Europe wide train timetable.