>What's the equivalent of drive C:\?

On Windows, partitions have labels like C, D, E and so on. There is no direct equivalent in Gnu/Linux. The a system like Trisquel does however allow you to open, inspect and manipulate partitions (like those on flash drives) like you'd expect on Windows. Such partitions/drives can be opened by clicking on their icon on the desktop or the file browser. That is all that is needed to use the system.

In case you want to know more, here's an example about how it works "behind the scenes": Let's say you've got a flash drive names "MyFlashDrive" with a file "MyFolder\MyFile.pdf" on it, and your username is "bob". On Windows, the absolute path to that file may be something like "H:\MyFolder\MyFile.pdf". When inserted into a computer running an OS like Trisquel, the system will automatically create a folder with an absolute path like "/media/bob/MyFlashDrive" and 'mount' the flash drive there. This just means that the folder becomes a 'doorway' into the flash drive. In that folder, you can see the contents of the drive and manipulate them. The absolute path to the file mentioned above would in this example be "/media/bob/MyFlashDrive/MyFolder/MyFile.pdf", the slash at the beginning indicates that it is an absolute path. This knowledge is usually not needed for everyday use.

>Equivalent of Program Files?

Nonessential executables are stored in folders like /usr/bin and /usr/lib, but it's unlikely you'll ever need to know this.

>How to launch .exe file?

Not sure how to interpret this question. Are you asking how to start a graphical application that was installed on a Gnu/Linux system? There's usually a startup icon for that in the GUI, on Trisquel they are in the main menu. Are you asking how to start an executable file that is not part of an application for some unusual reason? If it is marked as executable, simply opening it should work. Are you asking how to execute executables compiled for Windows? A compatibility layer like "Wine" can do that sometimes. I've heard there are some people using it to run Notepad++ on Gnu/Linux, which is a free software, GPL'd text editor that was only developed for Windows. I'd avoid using Wine however, it may not always work.

The file extension .exe is mostly only used on Windows. On Gnu/Linux, executables have no popular uniform extension.

>Is shell hard to learn?

It depends what you want to do, and how eager you are to learn.
For newcomers, I usually recommend Trisquel above most other distributions since it is one of the easiest to use. Ordinarily, you should not need to use the shell at all. On the internet, people will sometimes tell you to execute shell commands because it is faster than telling you how to navigate your way through a dozen windows, and it does not depend on which desktop environment or particular distribution you use.

>Something special I should know?

Maybe something about hardware. Hardware components like wifi chips and graphics cards require special firmware. Many of them are not properly supported by a system like Trisquel. Intel integrated GPUs (at least those that are not PowerVR-based) typically work best. Some Nvidia cards are mostly supported (I think it was the cards from the Fermi, Kepler and Maxwell (maybe also Tesla) series, but don't quote me on that), but they can be glitchy on very graphics-heavy applications. I did play some mostly successful experimental rounds of SuperTuxKart/0ad and some other games on one, though. Most other GPUs are not supported, at least not with graphics acceleration, which can be really painful.

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