In the case of Ashe, No - Not really.
Archery is an intensive sport, but not to the extent of creating extensive muscular growth.
Let's have a look at Linda Ochoa, currently 8th in the compound Archery scene.
http://www2.pictures.zimbio.com/gi/Linda+Ochoa+Archery+World+Cup+2015+Stage+1+W6qyLTKSNe6l.jpg
For the most part, she is not exceptionally ripped, her arms are definitely strong though.
As far as Arm anatomy goes, Ashe's arms are pretty up to par of what an IRL Archery professionals arms would be like.
Her body weight is disproportionate, but her arms are fine.
Sejuani on the otherhand yes, she should more then likely see an increase in muscle tone.
Let's have a look at Olympic Ball chain thrower, Betty Heidler
https://aos.iacpublishinglabs.com/question/aq/1400px-788px/much-hammer-hammer-throw-weigh_3c0505ad738481b9.jpg?domain=cx.aos.ask.com
This woman is built like a brick truck. It's important to take into mind, For this woman to throw the Ball Chain ONCE, she is required to be built like this. Your average Ball Chain weighs up to 35lbs, and Sejuani's flail would be a LOT heavier that that and she's swinging that thing over 6 times a minute.
(Betty is NOTHING but muscle btw.)
https://dz0obzljr6jvm.cloudfront.net/media/image/ef/e1/cd/betty_heidler_galerie_2.jpg
(Don't Olympic athlete's make the funniest faces???)
Some might call it out as Betty's genetics, but that's not the case. This body type is consistent amongst intensive sport players, from Shotput, to Ball Chain to Javelin, these body types are consistent.
https://s-media-cache-ak0.pinimg.com/originals/13/6c/9f/136c9f95da7560f2f2ba058718b9463e.jpg
https://s-media-cache-ak0.pinimg.com/736x/f1/35/59/f135592f6aa72fa0bcf7a51b410d7211.jpg
It's also important to note, that unlike weightlifters, Olympics Athlete's bodies are made for function, not just for show.
TL;DR: Ashe's body is fine save for some body weight issues. Sejuani should be built a lot stockier however.