Is it your PA, or a venue's PA, or will it be a mix at different times?
To understand where the different signal options for the two XLRs are taken from, have a look at the block diagram on the last page (11) of the manual.
https://static.roland.com/assets/media/ ... ng04_W.pdf
For the 'DI' output setting, the signal is taken after the pre-amp and input volume controls, but before any EQ or effects.
For the 'Post-FX' setting, as it says, the signal is taken after the preamp, EQ and effects , but before the mic and guitar signals get mixed together and fed into the looper section (which may be on or off).
The 'Mix' setting is taken after the looper and includes any signal from the Aux input there may be.
So you can have a single cable going to the PA from either the guitar or mic DI output with it set to 'mix'. What I don't know, as the manual annoyingly doesn't say, is what level the two XLRs output at. The mic and guitar outputs may be at mic level, though they are probably at line level. Assume line level and if the signal is very weak, then try a mic input on the mixer.
For FOH signals, if you've got someone mixing FOH for you, then it's always better to take individual mic and guitar signals as the sound guy really wants individual level control of the vocal and guitar signal, plus the ability to EQ them for the FOH system separately.
Whilst the harmony function needs to be under your control, if someone else is mixing, then it's best to keep the signals as flat EQ-wise and as free from reverb and delay as possible (unless you are occasionally using delay as a special effect and not an 'always on' effect). Again, you don't know what it sounds like out front, so the sound guy needs to make sure there's not too much reverb etc. If the room is already quite echo-y, then you don't want a lot of reverb in the mix. It's never a one-size-fits-all setting.
Of course if it's just you and a couple of PA speakers, then you could feed right and left speakers directly from the ACS outputs with both in 'Mix' mode. But you still need to go about front and see what it sounds like in the venue as it's going to sound very different to you a few feet in front of the amp.