Heck yeah - that is the exact setup I have in the livingroom here - a Scarlett 2i2 and Voicemeeter.
Right - set the A1 item to "ASIO Focusrite USB 2.0 Audio Driver" and it will take on the buffer settings of the 2i2. Those are adjustable by typing "Focusrite" in the Windows button search and it will show "Focusrite USB 2.0 Audio Control Panel" - which is pretty minimal. Now your monitoring output is set, and the whole system follows the ASIO buffer settings.
If you are sending the two outputs on the back of the Focusrite to an amp, keep in mind that the big knob will also control its output. That has no effect on the ASIO outputs, however. They get their signal from that A1 selection.
So, in slider one, you want to have it set to nothing at all, and it will adapt and show "A1 ASIO Input (1+2)" - that is your mic coming in through the 2i2. (I'm assuming that's what you want. That's how I have it set up.) If you want a single mic in the "center" click the "Mono" button. Slider 2 can be whatever - even a virtual cable.
The A buttons are for "Auditioning" or monitoring and the B buttons are for "Broadcast". Just remember that and you'll keep your head straight! The two output systems are entirely separate. If you are using Voicemeeter Pro "Banana" then there are two B outputs - a B1 and a B2, since that version ads a second virtual out called an "Aux".
Regular Voicemeeter just has the B button with one output - the VAIO (Virtual Audio In/Out). If you have Voicemeeter set as your default recording device in Windows, then it will get its signals from there. Likewise, having Voicemeeter as the default playback device in Windows makes your YouTube videos and media players play through that VAIO slider.
Keep your inputs and outputs separate in your mind! That is a source of confusion for many, since one slider is handling input level, but naturally affects the output level, so people think it is an output slider. But the output sliders are on the far right. The A ones handle the monitor volume and the B ones the output to your Focusrite ASIO output as well as to the Windows Recording default input if you have it set that way. (I would and do!)
So, you'll want typically the VAIO slider (and VAIO Aux if used) set to both A and B selected. I usually only have the A lit for the mic while checking stuff - there is a bit of latency that I'm not fond of hearing, so I don't bother monitoring the mic, but just send it out B.
Now, finally Cantabile and other ASIO friendly DAWs will see Voicemeeter as an ASIO device, and also as an ASIO Insert device, which is setup in Voicemeeters settings at the bottom of the "System Settings/Options" dialog. I'd leave that alone till you are comfortable with the basics! It is a pre-(Voicemeeter) fader insert system.