First of all Mahoutsukai Sally was the first anime directed to the Shoujo demographic. And when it comes to shoujo demographic in the 60s the manga scene there was already some kind of identity to the shoujo character design. You can see reminiscence of that design in the designs of the characters of this series.
The story of the series is simple at its core Sally coming to earth to live with the humans, however I don't think the series is necessarily about the overarching story. The story is moreso used as a vehicle to create the premise that enables setting up the characters. I'd say the important part of the story is the premise in which we learn that Sally doesn't have knowledge about the human world and comes to human world to start living in there.
The series however shines when it comes to the episodic slice of life stories based on around Sally learning about herself and the human world and what it means to be able to or to not use magic in human world. Which I think is explored in interesting ways throughout the series.
Art of the series gives off this cute and endearing vibe reminiscent of the 60s shoujo manga. I'd describe the overall visual aesthetic of the series as charming.
Voice acting in the series is pretty much the best voice acting that I've heard in any series. Especially when it comes to the main character Sally. Her voice gives off this cheeky yet endearing vibe that gives incredible amount of life into her character. Other voice actors don't fall far behind as the whole main cast gives off a really strong presence with their voices.
About the characters I'd say that this series has probably the best dynamic between characters that I've seen in any series. The dialogue and interaction between characters is joy to watch and listen with the lively voice acting coupled with visually endearing animation. It is a type of series where the characters grow on you the more you watch. More of the cast like Poron are introduced later on the series other than that the cast stays pretty much the same.
I'd say that the inclusion of Poron in the latter half of the series definitely enhanced the character dynamics of the series to a new level. As the Sally and Kabu duo dynamic didn't provide as much as it does as a trio with Poron.
Other important characters, Sally's 2 friends Sumire and Yoshiko with the triplet little brothers provide important perspective as major characters from earth. They are not aware of the magic that Sally has which I'd say adds another layer to the dynamic between the characters.
Overall I found the series, especially the interaction between the characters and the handling of the concept of magic very enjoyable on the series. I'd go as far that I say that the series has the best interpretation and starting point when it comes to exploring magic that I've seen when it comes to anime. When you combine that with the likable, charming and endearing overall vibe of the characters themselves and the design, you get something special.