For working on Lionel postwar, a copy of Greenburg's "Repair and Operating Manual for Lionel Trains 1945-1959" is a near must. Not necessarily a how-to book, but an exploded view, and parts list for most everything Lionel made during that era. Search this site for good reputable parts dealers if you need parts.
YouTube can be your friend for watching how others work on their trains. Some really know what their doing, others not so much. Use good judgement. You might get lucky by typing in your exact engine number in to YouTube and getting repair videos. There are some good groups on Facebook if you're into that.
Start with general maintenance, disassembly, cleaning and lubrication. Learn how to keep them running. Plenty of videos of that online. Learn about proper cleaning and lubrication products. Good advice here on OGR.
Beyond that, invest in some simple but quality tools, miniature screwdrivers, pliers, wire cutters, strippers, tweezers. I have a set of small combo wrenches normally used on carburetors that really help. Get a decent soldering iron and learn how to use it. Learn how to replace frayed and cracked-insulation wiring, replace brushes, rebuild smoke units, replace headlights.
Beyond that, start to lay in some specific repair tooling. A decent arbor press. Good used ones can be had cheap. Proper riveting and wheel pressing tools. Lean how to rivet pickup shoes, overhaul E-units, remove and press on wheels properly with proper tooling, rewind armatures. Get A good tap and die set.
Beyond that, get an airbrush and learn to use it. Learn about proper paint stripping and applications, and sources for good paint, and proper sources for decals and graphics. Lots of advice here on OGR for the searching.
Beyond that, get yourself some hobbyist machine tools and learn to use them. How to make some simple repair parts no longer available, bearings, bushings, fiber boards, etc. Make your own repair tooling and fixtures.
When I started repairing trains I was overzealous and impatient and didn't have skills or tooling. My early attempts made me frustrated and wanting to almost quit the hobby. I've tried to use the steps above, adding patience, and have tried to lean good practices to get and keep stuff running. I work on trains mostly in the winter when it's bad weather outside. I've overhauled a few ZW's and a handful of postwar steamers. I've currently overhauled two postwar locomotives this season (Lionel 2333 NYC and Lionel 1862 General) and have two Lionel 221's almost ready for paint, with the motors overhauled and ready to go.