Have you connected your Android devices to your computer in question and had them show up in Windows Explorer? If so, you'll also likely see them in the Drives and Devices subsection on the left. If that Android device also has a microSDXC/HC card in it, you'll see two entries. One for the phone storage, and one for the card storage. Right click on it, and you'll be able to pick playlists to sync and where to store the music. The default is for it have Music and Playlist directories on the root of the device. I sync mine to my microSDXC card because it's 64 GB, and I'll move to a 128 GB fairly soon.
As for the file types, you'll see a list of accepted types and can edit those. I add ".m4a" and ".aif;.aiff" to mine. You can then adjust the encoder properties to convert whatever files are in the playlist or library into a certain format (such as MP3). In my case, I just configured it to not transcode anything and use whatever the native format is, since I have applications that play my AIF and FLAC files (which I prefer) anyway. As a side note, the Samsung devices have supported FLAC files natively for a while, and my Note 3 plays them just fine in the stock application as well as the others.