When Agnes leave at 4pm, we will for the first time switch on the TV and Nienke will watch a bit of Heidi or Lollos. Or we'll play outside on the trampoline (Sion LOVES me holding him and jumping on trampoline) or we'll go to the shops or something like that.
Hubby gets home some time after this. (I hear you ask when do I make food? Hmmmm.... I rarely do. But I'll put on a stew earlier the day. I normally make the food earlier while Agnes is here and then we just heat it up.)
Bathtime is 6:30. I bath them both together. Sion sits in a bath chair and they LOVE bathing together. Sion is CRAZY about bathtime. I promise you, when it nears bathtime and we don't take them to be bathed, he starts moaning! Can you believe it!
I take Nienke out first, put towel around her, take him out. We then go to her room where I dress them both. Sometimes they are both screaming. You know a baby hates being dressed. It happens. But he has to be dressed, so I just continue throughout the screaming...
Some nights I can settle Nienke with a book in her bed and she falls asleep. Other nights hubby takes over with Nienke. But i always feed Sion after bedtime and then he sleeps. After that Nienke sometimes stay awake another hour (depending on nap she had) and I sort of just let her be. By this time you are quite tired, so if she wants to hang around, whatever.

We have to lie with Nienke as well but since she is now in her own room, she falls asleep while we go "fetch" her something. GREAT!
Shopping is also another story. When Sion was little, I put him in a Babysense sling and put NIenke in the trolley. So pushed trolley with Sion sleeping in sling. Now I put him in a kango pouch facing outwards. Works great! If he's asleep, I put his carseat in a trolley and put Nienke in a trolley. There's then just no space for groceries!
I love having two kids. Yes, everything is chaos. But it's lovely chaos. Some days I do get a bit run-down but mostly it's fun. They love each other and both are easy kids. I still feed Sion two to three times at night but am used to it by now. Nienke sleeps through.
So basically: just wing it the first few weeks, be kind to yourself, sleep enough and then you will find yourself settle into a routine.
Ps. I work from home. When? F knows! I schedule my interviews in the morning when Nienke is at school. I have Agnes, who is worth gold. I work at night after they both went to bed. The reason why I won't be writing exams (I am studying again through Unisa) is because as you can see there's no time at the moment to study! Sadly I still find time to eat.