Using timed access control in airport extreme base station

You've done the most important optimization available by placing the database files (the iTunes library files) on the local drive. If you had that on slow storage (and Airport Extreme is in the slow category as far as network storage) then I could see you having slow launch times.

Even a library with 70,000 items stored in it should only have an iTunes Music Library.xml file that takes about 120 MB of space which should load in less than 10 seconds unless your PC is really bogged down with other tasks on the CPU.

The actual size of all the media doesn't affect the application launch time as it only has to parse the library files and not check each and every file before you can start using the program.

I would look at tuning up the PC or speeding up the filesystem where the library files are and see if that results in better app performance.

Have you tried the automatic configuration for the Express?

Don't do anything on the Time Capsule.

Do a cold reset of the express and bring it up on the Airport Utility. You should have an option to join an existing Airport network. Choose the option to extend the range. That should do it.