I know all about the witching hour! I work full time, so when I pick my daughter up from school... watch out! She's excited to see me, so she's all hyped up, but I have to get dinner on, let the dogs out etc. I spent a lot of time feeling guilty about not giving 100% of my attention to my daughter right away and stressed out that I had to get so many things done, but I finally realized that I'm not perfect, so why do I try to make it that way? Luckily for me, my dh is pretty laid back, so he doesn't care if we have a big meal every night, so I stopped making big meals every single night. He's perfectly happy w/ a simple salad or ordering pizza most week nights and then I cook a big dinner on the weekends. When I do cook dinner during the week, I let my daughter watch a tv show, color at the table or do playdoh while I cook. The dogs get put out back & walked later in the night. After dinner my daughter gets 100% of my attention to play, read, etc until I give her a bath and put her in bed. She's happy and I'm happy and a lot less stressed out. When it's nice out, we'll sometimes take a walk/bike ride around the block as soon as we get home and that calms her down too. It's what works for us.
Good luck!